The proposition of click chemistry has provided a quick channel for saccharides modification, which has always been worth exploring. Click reaction of hydroxyl groups possessed by saccharides is thus highly desirable to be developed. In this paper, we report hydroxyl-yne click polymerization using ester activated alkynes and alcoholic hydroxyl groups. The polymers, poly(vinyl ether ester)s (PVEEs), were obtained with high weight-average molecular weights up to 71 000 were obtained in excellent yields up to 99% using a commercially organic base of bicyclo[2.2.2]-1,4-diazaotane (DABCO) as catalyst under ambient conditions. The obtained polymers possess high thermal stability and low cytotoxicity. Both semi-crystalline and amorphous polymers were obtained due to the different flexibility of monomers. Upon incorporating aggregation-induced emission (AIE) moiety of tetraphenylethylene (TPE), the resultant polymers displayed typical AIE characteristics. This work provides a potential strategy for saccharides modification via the hydroxyl-yne click reaction.