AbstractA novel hybrid resist for UV nanoimprint lithography (UV‐NIL) based on the thiol–ene photopolymerization is presented. Our system comprises mercaptopropyl polyhedral oligomeric silsesquioxane and benzyl methacrylate, with trimethylolpropane trimethacrylate as the crosslinker. The obtained hybrid resists possess a variety of characteristics desirable for UV‐NIL, such as low viscosity (6.1–25 cP), low bulk‐volumetric shrinkage (5.3%), high Young's modulus (0.9–5.2 GPa), high thermal stability, and excellent dry‐etch resistance. Based on these performances, the optimized components are evaluated as UV‐NIL resists. The result is a high‐resolution pattern with feature sizes in the range of 100 nm to several microns. The double‐layer resist approach is used for pattern transfer into silicon substrates. The excellent oxygen‐etch resistance of the barrier material enables a final transfer pattern that is about three times higher than that of the original NIL mold.