David, the electoral college was created by the Constitution. In the first election under the Constitution, the electoral college unanimously elected George Washington.
Here is the wikipedia article:
http://en.wikipedia.org/wiki/United_States_presidential_election,_1789
They also elected John Adams Vice-President, but this was not unanimous.
This was the first time the electoral college ever voted, because they had only just been created by the new Constitution.
How are you saying Washington became President of the United States in OTL? (Are you talking about a different timeline where he becomes President some other way?)
KEVP