According to one website this exclamation became quite popular in super hero comic books although a possible early origination of "Great Scott" might be the German exclamation "Gruess Gott." Source(s):
http://www.answers.com/topic/great-scott-1 William Wallace I think they may be referring to any scottsman (a scottish person), as they have a reputation for being of large stature. Or it could be Sir Walter Scott, as in the writer of Rob Roy and Ivanhoe.
I changed my mind... Tara sounds like she has the right answer. :) There was indeed a famous American general named Scott, who did have the title of commander-in-chief of the US Army at the time of the outbreak of the Civil War, though he is best known as one of the two American heroes of the Mexican War of 1846–48 (if, that is, you’re American and not Mexican). This was General Winfield Scott, known to his troops as Old Fuss and Feathers. It seems plausible that he is the source being pointed to, especially as in his later years he weighed 300 pounds (21 stone or 136kg) was too fat to ride a horse and was certainly a great Scott in a very literal sense.
There’s nothing new in this attribution, however. Winfield Scott has previously been fingered as the origin by several writers, among them Eric Partridge. And we still can’t be absolutely sure that he was the Scott being alluded to. But the combination of dates and the references written so soon after the event point to him quite strongly. Scott the Great, of course!
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