Extraterritoriality is the longest word in the English language beginning with "ex."
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The longest word starting with E is Electroencephalographically.
Floccinaucinihilipilification is the longest word starting with F; it means the act of estimating something as worthless.
Pneumonoultramicroscopicsilicovolcanoconiosis (also happens to be the longest word in the English language)
The longest word starting with a "P" is pneumonoultramicroscopicsilicovolcanoconiosis, which has 45 letters and is in the Guinness Book of Records. It was, however, coined for the specific purpose of becoming the longest word, and is not a specifically recognized form of silicosis.
forethoughtfulness