The chemical upcycling of waste plastics has emerged as a cornerstone of ecological development and the circular economy. However, the high entropy of polymers during chemical conversion severely limits catalytic activity, emphasizing the urgent need to establish robust polymer–catalyst interactions to mitigate entropy-related constraints. Herein, we present a universal entropy-reduction engineering strategy that optimizes polyolefin–catalyst interactions via a novel surface polarity reconstruction method. By modifying catalyst surfaces with coupling agents, this approach effectively restricts the molecular freedom of polyolefins during hydrogenolysis, enabling stable transition-state adsorption on the catalyst surface and facilitating the efficient conversion of waste polyolefins into liquid fuels. Beyond improving the performance of various supported metal catalysts, this strategy achieves the efficient and stable hydrogenolysis of diverse polyolefin wastes, including commercial samples, demonstrating significant industrial application potential and advancing the sustainable upcycling of polyolefins.