The influence of ammonium polyphosphate (APP) on the smoke emission of poly(acrylonitrile) (PAN) has been examined, and its mechanism of action as a smoke suppressant agent has been investigated. Smoke density and corresponding residual char data, as a function of temperature, were obtained in order to characterize the smoke propensity of PAN. The amount of generated smoke, both in smoldering and flaming conditions, was considerably lowered by the presence of APP, and higher char yields were obtained. Beside the smoke suppression, flame inhibition effect of APP on PAN was evidenced. Thermogravimetry (TG), oxygen index (OI), and nitrous oxide index (NOI) experiments were also performed. On the basis of our data, APP appears to act as a char-forming agent in PAN combustion. Both smoke suppression and flame inhibition effects can be considered a consequence of this action.