I very clearly remember this from the Word-a-day calendar my boyfriend in college had. This calendar taught us two very interesting words, the meanings of which I still remember.
The words were sesquipedalian and defenestration.
Sesquipedalian means "of or pertaining to a foot and a half," and defenestration means "throwing something out a window."
Of course, words can have more than one meaning. Sesquipedalian has come to mean "given to using long words" or even referring to long words themselves. If you look at the Latin parts you can see where my first definition above came from. Despite opinions to the contrary, sesquipedalian is not the longest word in the English language, though I did find a blog post describing it as a $10 word. Does that mean I can earn $10 by writing about it? This post should be worth $20.
Sesquipedalian came up in a little vocabulary game called Match Up that I have as a widget on my iGoogle page. They give you 2 groups of 5 words and you have to match the synonyms. Each day, a new set of 5 pairs. A computer obviously picks them, because it's pretty obvious, even if you don't know what it means, that sesquipedalian and sesquipedalia have to be synonyms.