Green monomers, such as carbon dioxide (CO2), are closely related to our daily life and highly desirable to be transferred to functional polymers with diverse structures and versatile properties because they are abundant, cheap, nontoxic, renewable, and sustainable. However, the polymerizations based on these green monomers are to be further developed. In this work, a facile CO2 and alkyne-based one-pot, two-step, four-component tandem polymerization was successfully established. The polymerization of CO2, diynes, alkyl dihalides, and primary/secondary amines can proceed under mild reaction conditions and regio- and stereoregular poly(aminoacrylate)s with good solubility and thermal stability were obtained in high yields (up to 95％). Notably, distinctly different stereoregularity of resultant poly(aminoacrylate)s was realized via using primary or secondary amines. Using the former would readily generate polymers with 100％ Z-isomers, whereas the latter furnished products with over 95％ E-isomers. Through different monomer combination, the polymers with tunable structures and properties were obtained.Moreover, the tetraphenylethene units containing poly(aminoacrylate)s, showing the unique aggregation-induced emission characteristics,could function as a fluorescent probe for sensitive explosive detection. Thus, this work not only develops a facile CO2 and alkyne-based multicomponent tandem polymerization but also provides a valuable strategy to fine-tune the polymer structures and properties, which could be potentially applied in diverse areas.