Membrane proteins play crucial roles in fundamental biological processes. Here, we propose a new chemical strategy to label and characterize membrane proteins on cell surface. In this study, 4-dimethylaminopyridine (DMAP) is embedded and concentrated on plasma membrane surface (biomembrane-embedded DMAP: BeD), allowing to selectively modify membrane proteins with synthetic probes such as a fluorophore and an affinity tag. We applied this strategy to human red blood cells, which demonstrated that membrane proteins such as PAS-1 and Band-3 were selectively labeled.