Chancellor Sebastian Kurz announced the decision in a Spanish-language tweet on Monday after President Nicolas Maduro ignored an ultimatum to call a new election.
Kurz said Guaido, who heads the opposition-controlled National Assembly, has "our full support in his efforts to re-establish democracy in Venezuela."
French President Emmanuel Macron says he recognizes opposition leader Juan Guaido as interim president of Venezuela and urges him to hold a new presidential election shortly.
Macron also declared that Venezuelans "have the right to express themselves freely and democratically."
Moments after Foreign Minister Jean-Yves le Drian said France is recognizing Guaido, Macron posted a message on Twitter on Monday to express his support for the head of the Venezuelan congress.
At least eight other European nations did the same on Monday after current Venezuelan President Nicolas Maduro defied their call to resign and hold a new vote. Sweden said the vote that brought Maduro to power was not free or fair.
Germany has joined other European nations in recognizing opposition leader Juan Guaido as Venezuela's interim president.
Germany and several other countries in the European Union had given Venezuelan President Nicolas Maduro's government an eight-day deadline to call a new presidential election. That ultimatum expired on Sunday.
German Chancellor Angela Merkel said during a visit to Japan on Monday that Guaido "is the legitimate interim president."
Germany joins Spain, Britain, France, Sweden, Austria, Denmark and Lithuania in recognizing Guaido on Monday. He also has the support of Washington and most South American nations.
Guaido, who heads the opposition-led National Assembly, declared himself Venezuela's legitimate ruler on Jan. 23.
Venezuelan President Nicolas Maduro is remaining defiant amid European Union pressure to stand down and is accusing the United States of preparing a coup in the South American country.
Maduro told Spanish TV channel La Sexta in an interview broadcast late Sunday that he "accepts ultimatums from nobody," amid demands by some EU countries that opposition leader Juan Guaido take over.
The Trump administration has also backed Guaido, after he declared himself the interim president of Venezuela on Jan. 23.
Maduro says "the military option is on (U.S. President) Donald Trump's table."
He accuses the U.S. of "wanting to return to the 20th century of military coups, subordinate puppet governments and the looting of resources."
Washington recently imposed sanctions on Venezuelan oil exports in an effort to undermine Maduro's main source of income and weaken his grip on power
Swedish Foreign Minister Margot Wallstrom says the election that brought Venezuelan President Nicolas Maduro to power was neither free nor fair.
In an interview Monday with Swedish broadcaster SVT, Wallstrom said Venezuelans "now must get new, free and fair elections instead."
She said "we support and consider Juan Guaido and the National Assembly as the only legitimate representatives of the Venezuelan people" — a move made by several European Union nations on Monday.
Wallstrom also says "Venezuela is a country in disrepair. There is a lack of food and medicines, it's (facing) inflation and mass demonstrations."
Guaido declared himself Venezuela's legitimate ruler on Jan. 23 and has the support of Washington and most South American nations.
Spanish Prime Minister Pedro Sanchez says his government is endorsing Juan Guaido as interim president of Venezuela and is urging him to call a presidential election as soon as possible.
Sanchez on Monday carried out his threat to recognize Guaido's leadership if embattled President Nicolas Maduro hadn't called a presidential election by Sunday.
Other European Union countries followed suit, a week after the European Parliament has called on the EU's member states to recognize Guaido as Venezuela's interim president.
Spain has strong historical, cultural and economic ties to Venezuela, and its support for Guaido is a diplomatic blow to Maduro.
Sanchez says, "we are working for the return of full democracy in Venezuela: human rights, elections and no more political prisoners."
He says Spain is also working on a humanitarian aid program for Venezuela.
Britain has joined Sweden and France in recognizing Juan Guaido as the interim leader in Venezuela.
U.K. Foreign Secretary Jeremy Hunt says in a tweet that Venezuelan President Nicolas Maduro had not called for a new presidential election within the eight-day time limit set.
He tweeted that the "UK alongside European allies now recognises @jguaido as interim constitutional president until credible elections can be held. Let's hope this takes us closer to ending humanitarian crisis."
Opposition leader Guaido declared himself Venezuela's legitimate ruler on Jan. 23, and has the support of Washington and most South American nations.
Spain, France and Sweden have all announced that they are recognizing Venezuelan opposition leader Juan Guaido as the country's interim president and are urging him to hold a new presidential election.
Spanish Prime Minister Pedro Sanchez told reporters in Madrid on Monday that "we are working for the return of full democracy in Venezuela: human rights, elections and no more political prisoners."
French Foreign Minister Jean-Yves Le Drian, speaking Monday to France Inter Radio, urged Guaido to call an early presidential election that will ensure "the Venezuelan crisis ends peacefully."
Swedish Foreign Minister Margot Wallstrom told Swedish broadcaster SVT the vote that brought Maduro to power was not a "free and fair election."
Venezuelan President Nicolas Maduro has so far rejected calls by European countries to call an early election.