Catalytically active membranes can realize chemical reaction and membrane separation simultaneously and have been recognized as an effective strategy for process intensification to offer smaller footprint, lower energy consumption, and enhanced process efficiency. Reaction-separation coupling involving high temperature reactions has traditionally evolved around inorganic membranes. However, great advancements have also been achieved on development of more versatile and abundant polymeric catalytically active membranes (pCAM) for a range of niche applications. This review is the first attempt to provide an overview of reaction-separation coupling by pCAM. Liquid phase reactions often occur at mild temperatures and the majority of studies dealing with pCAM are focused on these reactions. Research progress of reaction-separation coupling using pCAM for liquid phase reactions including fine chemical synthetic, photocatalytic and biocatalytic reactions is first examined. The limited studies on the use of pCAM for gas phase reactions are also summarized. Perspectives on the future development of pCAM and their potential applications are also highlighted.