A chemoselective polymerization platform was designed for flow synthesis of telechelic thiol-functionalized polymers, amphiphilic block copolymers and noble metal nanoparticles. By assembling Novozyme435 packed tubular reactor, a-thiol-.-hydroxyl telechelic poly(epsilon-caprolactone) were efficiently obtained via metal-free and protecting-group-free ring-opening polymerizations. Fast polymerization, high end group fidelity, controlled molecular weight and distribution were achieved under the flow conditions. The resultant mercapto-polymer solution derived from the enzymatic process was directly pumped into the subsequent microreactor system (isolation-step-free) to prepare amphiphilic poly(N-vinylpyrrolidone)-block-poly(epsilon-caprolactone). Relative narrower molecular weight distribution was observed in contrast to the batch mode. Moreover, silver nanoparticles were facilely fabricated in flow fashion by using mercapto-polymer solution as the stabilizer without isolation. The surface plasma resonance band absorption of nanoparticles could be adjusted by regulating the flow rates. This chemoselective polymerization platform would provide a powerful toolbox for the novel polymer and nanomaterial preparations.