Yes. In fact, there was one president for whom English was a second language. President Martin Van Buren came from a Dutch family, and thus learned Dutch as his first language. He was also the first president not from a British or Irish background.

Jimmy Carter speaks Spanish well enough to do a portion of his address to the Mexican Congress in that language. Jefferson of course was able to be US ambassador to France and operate in that language. I bet he could have made a bad at accented Latin too.

Wikipedia has a good, although I believe incomplete list of multilingual presidents: http://en.wikipedia.org/wiki/List_of_multilingual_Presidents_of_the_United_States

I say incomplete because it's my understanding that John Adams could also read hebrew.

Wasn't it either Cleveland or Hoover that spoke mandarin fluently?