Using carbon dioxide (CO<sub>2</sub>) 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 CO<sub>2</sub>-based
luminescent polymers. In this work, we successfully developed
a new one-pot MCTP combining three sequential
carboxylation-cyclization-esterification reactions of CO<sub>2</sub>, diynes
and alkyl dihalides to direct fixing CO<sub>2</sub> into luminescent polymers with
aggregation-enhanced emission (AEE) property. This MCTP could be
facilely carried out in <i>N,N</i>-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(<i>β</i>-alkoxyacrylate)s with
well-defined structures, high molecular weights (<i>M</i><sub>w</sub> 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(<i>β</i>-alkoxyacrylate)s with AEE features. Thus, this work
provides a new pathway to directly transform CO<sub>2</sub> into luminescent
polymers via a one-pot MCTP strategy.