"Defenestrate" - to throw someone or something out a window - seems to be one of everyone's favorite words. It's simultaneously simple in its directness, and a bit sesquipedalian. The etymology isn't exactly a mystery. It's the simple combination of a latin prefix with a latin noun. But why did this word attain common English usage? You could create other words in this fashion just as easily. How about detabernated - to be have been forcibly ejected from a bar? But nobody, alas, uses that word.
It seems that defenestrate hit the English scene around 1618, when two imperial commissioners were thrown from a window of the palace in Prague, having been found guilty of violating religious rights. The event was dubbed the Defenestration of Prague, and instigated the Thirty Years War. The universal pleasure of appropriately using "defenestrate" in a sentence has ensured its permanent place in the English vocabulary.
In a mostly unrelated feat, I'll now use three of my favorite big words in one sentence.
Despite her avoirdupois, or perhaps because of it, the callipygian singer cum actress was widely considered to be pulchritudinous.
And if I had been able to find a way to get "lagniappe" (free with purchase) into that sentence, you can bet your finely developed buttocks I would have.