AbstractPolyolefins comprise a major fraction of single-use plastics, yet their catalytic deconstruction/recycling has proven challenging due to their inert saturated hydrocarbon connectivities. Here a very electrophilic, formally cationic earth-abundant single-site organozirconium catalyst chemisorbed on a highly Brønsted acidic sulfated alumina support and characterized by a broad array of experimental and theoretical techniques, is shown to mediate the rapid hydrogenolytic cleavage of molecular and macromolecular saturated hydrocarbons under mild conditions, with catalytic onset as low as 90 °C/0.5 atm H₂ with 0.02 mol% catalyst loading. For polyethylene, quantitative hydrogenolysis to light hydrocarbons proceeds within 48 min with an activity of > 4000 mol(CH₂ units)·mol(Zr)⁻¹·h⁻¹ at 200 °C/2 atm H₂ pressure. Under similar solventless conditions, polyethylene-co−1-octene, isotactic polypropylene, and a post-consumer food container cap are rapidly hydrogenolyzed to low molecular mass hydrocarbons. Regarding mechanism, theory and experiment identify a turnover-limiting C-C scission pathway involving ß-alkyl transfer rather than the more common σ-bond metathesis.