Organophosphorus (an organic compound containing phosphorus) has 16 letters.
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Overenthusiastically or Overapprehensiveness Both are 20 letters long :D
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)
Extraterritoriality is the longest word in the English language beginning with "ex."