Floccinaucinihilipilification is the longest word starting with F; it means the act of estimating something as worthless.
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forethoughtfulness
firetruck
The longest word starting with E is Electroencephalographically.
Pneumonoultramicroscopicsilicovolcanoconiosis (also happens to be the longest word in the English language)
Extraterritoriality is the longest word in the English language beginning with "ex."