Hecto- is the Greek root for 100, centi- is the Latin root for 100.
The metric prefixes up to 1000 use Greek roots for the large prefixes (10^+n) and Latin for the small (10^-n), but there are also words that are derived directly from the respective Latin roots and therefore don't necessarily carry the metric system's fractional meaning.
Someone already linked to the definition of centimillionaire, but here are a few more:
* centipede (100 legs, not 1/100 of a leg)
* centenarian (100 years old, not 1/100 of a year old)
Reminds me of how financial newspapers often use a small "m" when describing millions of something. "$500m", or even worse "500m USD"... The engineer in me says that's 50 cents!
I know it is a word people use, and "centi-" is ambiguous without no context, but it's extremely unambiguous in the context of units of measure, and the word "hundred-millionaire" already existed and had the same number of syllables, so it's a really awkward choice.
They have $10,000?