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4 words rhyme with optimism, all of them 4-syllable words. A rhyme is matched on the phonemes from the last stressed vowel onward — for optimism that is MIHZAHM — so every word below genuinely rhymes when spoken, whatever its spelling suggests.
Two words rhyme when their pronunciations agree on every phoneme from the last stressed vowel to the end of the word. Nothing about spelling is consulted — that is why eight rhymes with freight and straight, and why cough rhymes with none of though, through or bough. For optimism the matched ending is MIHZAHM. The key is the pronunciation from the last stressed vowel onward, written in the CMU Pronouncing Dictionary's phoneme alphabet. Every entry sharing it rhymes.
The list below is grouped by syllable count, one-syllable words first, and ordered within each group by how often the word appears in everyday English. It is not filtered for quality or for near-rhymes: everything here is an exact match on the rule above, and nothing that matches has been left out.
Pronunciations and rhyme keys come from the CMU Pronouncing Dictionary; definitions and commonness come from WordNet and a corpus of everyday English. Full sources and licences.