Regioseletive 1,3-dipolar polycycloadditions of 4,4′-isopropylidenediphenyl dipropiolate (1) and tetraphenylethene (TPE)-containing diazides (2) are carried out in polar solvents such as DMF/toluene at a moderate temperature of 100 °C for 6 h, producing poly(aroxycarbonyltriazole)s (PACTs) P3 with high molecular weights (M w up to 23900) and regioregularities (F 1,4 up to ∼90%) in high yields (up to ∼99%). These metal-free click polymerizations can propagate smoothly in an open atmosphere without protection from oxygen and moisture. The obtained polymers are soluble in common organic solvents and thermally stable at temperatures up to 375 °C. Thanks to their contained TPE moieties, the PACTs show aggregation-induced emission and can serve as fluorescent chemosensors for superamplified detection of explosives.