Achieving a harmonious combination of the efficiency of homogeneous catalysts with the reusability of heterogeneous catalysts is a fundamental and challenging problem. Metal nanoparticles in a suitable matrix offer a potential solution. However an ideal design is yet to be realized, because the critical requirements of facile access to the catalyst, its durability, and ease of retrieval and reuse are difficult to reconcile. We report herein a multilayer free-standing thin-film catalyst based on silver nanoparticles, generated in situ inside poly(vinyl alcohol) by using a facile protocol, which shows excellent efficiency and extensive reusability in the prototypical reaction, the reduction of 4-nitrophenol by sodium borohydride. The “dip catalyst” film, which can start/stop the reaction instantaneously by mere insertion/removal, is used 30 times leading to a total turnover number (TON) of ≈3390, which is unprecedented for this reaction. The efficiency of the catalyst is reduced only marginally at the end of these runs, promising further extended usage. The unique advantage of convenient catalyst monitoring is illustrated by the periodic spectroscopic and microscopic examinations of the thin film, which revealed the basis of its durability. The demonstrated potential of metal-nanoparticle-embedded polymer thin films, coupled with their versatility and ease of fabrication, promises extensive applications in chemical catalysis.