Using carbon dioxide (CO2) as a feedstock to synthesize various polymers has drawn much attention. One-pot multicomponent tandem polymerization (MCTP) with great synthetic simplicity and efficiency is a powerful strategy for the synthesis of new CO2-based luminescent polymers. In this work, we successfully developed a new one-pot MCTP combining three sequential carboxylation-cyclization-esterification reactions of CO2, diynes and alkyl dihalides to direct fixing CO2 into luminescent polymers with aggregation-enhanced emission (AEE) property. This MCTP could be facilely carried out in N,N-dimethylacetamide in the presence of a cheap catalyst CuI and an organic base 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene under atmospheric pressure. A series of poly(β-alkoxyacrylate)s with well-defined structures, high molecular weights (Mw up to 15 400) were obtained in high yields (up to 96%). The resultant polymers possess good thermal stability with high decomposition temperature and high char yield. Due to polymerization-induced emission (PIE) behavior, the non-luminescent monomers could be converted to luminescent poly(β-alkoxyacrylate)s with AEE features. Thus, this work provides a new pathway to directly transform CO2 into luminescent polymers via a one-pot MCTP strategy.