inflammable adj.

mid-14c., "make (someone) ardent; set (the spirit, etc.) on fire" with a passion or religious virtue, a figurative sense, from Old French enflamer "catch fire; set on fire" (Modern French enflammer), from Latin inflammare "to set on fire, kindle," figuratively "to rouse, excite," from in- "in" (from PIE root *en "in") + flammare "to flame," from flamma "a flame" (see flame (n.)).

The literal sense of "to cause to burn" first recorded in English late 14c. Meaning "to heat, make hot, cause inflammation" is from 1520s. Formerly also enflame, but since 16c. the spelling with in- has predominated. Related: Inflamed; Inflaming.

word-forming element meaning "not, opposite of, without" (also im-, il-, ir- by assimilation of -n- with following consonant, a tendency which began in later Latin), from Latin in- "not," cognate with Greek an-, Old English un-, all from PIE root *ne- "not."

In Old French and Middle English often en-, but most of these forms have not survived in Modern English, and the few that do (enemy, for instance) no longer are felt as negative. The rule of thumb in English has been to use in- with obviously Latin elements, un- with native or nativized ones.