Multifunctional hyperbranched polymers, as an important class of materials, are widely applied in various areas. Therefore, the development of simple and efficient reactions to prepare hyperbranched polymers is of great significance. In this paper, for the first time, a series of multifunctional hyperbranched poly(beta-aminoacrylate)s (hb-PAAs) were synthesized using our established spontaneous amino-yne click polymerization. Using the optimized polymerization conditions, soluble and thermally stable hb-PAAs with high weight-average molecular weights (M-w up to 18,290) were obtained in excellent yields (up to 99%). This click polymerization also can proceed in stereo- and regiospecific and anti-Markovnikov addition fashion, and 100% E-isomers were obtained. Moreover, introducing the aggregation-induced emission (AIE)-active tetraphenylethene moiety into polymer backbones endows the resultant polymers with unique AIE properties, and their nanoaggregates can be used for sensitive detection of explosives. This work not only enriches the family of hyperbranched polymers but also confirms the universality of the spontaneous amino-yne click polymerization.