So what could the diva and the diplomat have in common?
"We do have some things in common, but I am a democrat forever, let me be very clear about that, alright?" Franklin said laughing.
"Well, we're all Americans and President Obama is my president as well," Rice said. But there's much more to it than that.
For one, both are minister's daughters. And both are devoted to music.
That love of music brought the two to the same stage last night.
An unlikely duo, Franklin's powerhouse voice and Rice's prowess on the piano came together alongside the acclaimed Philadelphia Orchestra at the Mann Music Center to raise money for inner city music education.
Even though they're on opposite ends of the political spectrum -- Franklin is a Democrat, and Rice was a Republican president's secretary of state and national security adviser -- both women are in agreement about the importance of music.
"Music is critical for young minds because not only does it make you a well-rounded person, but it really does develop different cognitive pathways, different ways of thinking and learning," Rice told "Good Morning America."
Franklin said their partnership transcended politics.
"This is about making a social contribution. And it is purely from the artistic point of view that we come together," she said.
The two first met at a White House dinner, and while there, Franklin said she heard someone say that Rice played with a symphony.
"And I said 'Condoleezza Rice plays with a symphony? Plays what?'"
When she learned Rice played the piano, Franklin said, "This I had to hear."
In fact, Rice had given up a career in classical music to pursue her other passion: international relations. Even as she occupied one of the highest posts in the nation's government, she kept playing.
She accompanied world famous cellist Yo-Yo Ma in 2002 and has performed for Queen Elizabeth II of England.
"Music has always been a part of me," Rice, a classically trained pianist, told "Good Morning America." "I was 3 years old when I started playing the piano, and so I don't remember life without music."
Rice was asked if she missed the rough and tumble world of politics.
"Oh, I don't miss it in the least. Eight years was a long time," she said. "I loved it, I loved the time, I loved representing this great country. But I'm on to other things. I'm now a professor who's getting a chance to play in Philadelphia with the queen of soul! It doesn't get better than that."
Rice isn't the only one whose life has taken a different turn. Franklin, who has earned the moniker of the Queen of Soul, is getting ready to expand her musical horizons with the recording of her first album of classical music.
"It just allows me to express myself in a different way, down a different avenue," Franklin told "GMA" of the upcoming album.
She certainly isn't a stranger to classical music. In 1988, she filled in at the Grammy awards for Luciano Pavarotti.
Last night's benefit grossed $582,000. Depending on the night's success, the two may take their duet on the road.