A phosphorescence enhancement of pyridinium macrocycle/monomer phosphors is realized with up to 14.7-fold prolonging of the phosphorescence lifetimes and visible afterglow by doping into a poly(vinylalcohol) (PVA) matrix. The abundant hydrogen-bonding interactions and electrostatic interactions between the phosphors and the PVA suppressed the nonradiative decay processes, slowed down the radiative decay and nonradiative decay of triplet states, and therefore promoted the long-lived RTP.