There are a lot of demands to develop abundant superior properties of aggregation-induced emission (AIE) polymers used in the aggregation state. Here we report a practical and versatile approach for the preparation of AIE polymers by conventional free radical polymerization. As an initiator, TPE-AZO has an excellent ability to initiate polymerization of various kinds of vinyl monomers to obtain AIE functional materials. It was found that TPE polymers emit multiple colors with wavelengths ranging from 370 to 482 nm, and they also exhibit the advantages of combining the AIE characteristic with unique properties of polymers. The fluorescence properties of temperature-sensitive TPE-PNI-PAM, pH-sensitive TPE-PMAA, and counterion-sensitive TPE-PMETAC were investigated, and the results indicated that all of the responsive behaviors of the three TPE polymers were related to the change in fluorescence. Our versatile approach would provide a platform to fabricate AIE polymers with various superior properties using the azo-based AIE molecular initiator under mild conditions.