Heiko Maas said he expressly asked Germany's ambassador to Venezuela, Daniel Kriener, to join other envoys at the airport on Monday.
He told reporters in Berlin on that "there was information that he (Guaido) was meant to be arrested there, and I think the presence of various ambassadors contributed to helping prevent this arrest."
On Wednesday, the government of Venezuelan President Nicolas Maduro announced it was giving Kriener 48 hours to leave the country, a move seen as a response to Germany's support for Guaido.
Maas said that "the decision by the Venezuelan government, or rather the Maduro regime in Caracas, to expel Ambassador Kriener as 'persona non grata' is in no way comprehensible or acceptable for us."
He added that Germany will continue to recognize Guaido as Venezuela's legitimate interim president and support him in holding fresh elections.