Here, the development of a new catalyst is reported for the selective furfural (FF) hydrogenation to furfuryl alcohol (FA) based on about 7 nm sized Pd−Cu alloy nanoparticles (NPs) formed in inexpensive, commercially available micro/mesoporous hypercrosslinked polystyrene (HPS). A comparison of the catalytic properties of as‐synthesized and reduced (denoted “r”) catalysts as well as Pd−Cu alloy and monometallic palladium NPs showed a considerable enhancement of the catalytic performance of Pd−Cu/HPS‐r compared to other catalysts studied, resulting in about 100 % FF conversion, 95.2 % selectivity for FA and a TOF of 1209 h−1. This was attributed to the enrichment of the NP surface with copper atoms, disrupting the furan ring adsorption, and to the presence of both zerovalent and cationic palladium and copper species, resulting in optimal hydrogen and FF adsorption. These factors along with exceptional stability of the catalyst in ten consecutive catalytic cycles make it highly promising in practical applications.