"a word of many syllables," by 1818 as a dictionary word, from multi- "many" + syllable. As an adjective, "consisting of or containing many syllables," by 1892.
Entries linking to multisyllable
multi-
before vowels mult-, word-forming element meaning "many, many times, much," from combining form of Latin multus "much, many," from PIE *ml-to-, from root *mel- (2) "strong, great, numerous." It was much-used in forming Latin compounds in classical times and after (such as multianimis "having much courage," multibibus "much-drinking," multicomus "having much hair," multiloquus "talkative"). Many English words that use it (multinational, etc.) are 20c. coinages.
syllable n.
late 14c., from Anglo-French sillable, alteration of Old French silabe "syllable" (12c., Modern French syllabe), from Latin syllaba, from Greek syllabē "that which is held together; a syllable, several sounds or letters taken together," i.e. "a taking together" of letters; from syllambanein "take or put together, collect, gather," from assimilated form of syn- "together" (see syn-) + stem of lambanein "to take" (see lemma). The unetymological -le apparently is by analogy with participle and principle.