A perylene-functionalized polycation was synthesized by quaternization of poly(4-vinylpyridine) with bromomethyl-perylene and methyl iodide, which exhibited a unique aggregation-induced emission (AIE) effect. The synthesized polycation and polyanion ssDNA could form a complex probe to detect DNA hybridization. Upon adding noncomplementary ssDNA, the fluorescence of the complex probe increased due to the AIE effect; upon adding complementary ssDNA, the fluorescence intensity changed little due to the combined effects of AIE and duplex-quenching resulting from the intercalation of perylene into the duplex.