We report the immobilization of unprotected silver nanoparticle on the carboxylic acid abundant polymer single crystal surface with controllable size through photogenerated chemical reduction reaction. The resulting silver nanoparticle decorated polymer single crystal not only shows higher catalytic activity as compared to its counterpart bearing surface ligand but also exhibits size-dependent catalytic activity with the smallest size (similar to 1.5 nm) being the most active. By further introducing iron oxide nanoparticles onto its surface, the resulting catalyst system can be magnetically recycled for up to five times with little loss in catalytic activity. These, together with the high loading originated from the high surface area to volume ratio for a polymer single crystal, make current catalyst system attractive for many industrial important catalytic applications.