The chemical inertness of polyolefin plastics poses a significant challenge to their efficient recycling. In this work, a Ru/TiO2-CNT catalyst is developed by engineering interfacial compatibility and dynamic active hydrogen pools to accelerate polyolefin hydrogenolysis. Enhanced interfacial compatibility between Ru and TiO2 optimizes the electronic state of Ru, thereby facilitating effective C−C bond cleavage. Meanwhile, dynamic active hydrogen pools, enabled by a reversible hydrogen spillover