Between the two pathways, hydrocracking is more favored at lower hydrogen pressure (PH2) and with more branched substrates. It accounts for the majority of polypropylene conversion at PH2 ≤ 30 bar on Ru/TiO2-A-SG, while is only important at 5 bar with low-density polyethylene and nhexadecane. With low dehydrogenation ability, hydrogenolysis suppresses hydrocracking by reducing free alkene concentration. The hydrocracking activity of Ni/TiO2-A-SG is higher than a Ni/SSZ-13 we tested, and its evolution with air exposure and calcination suggest that the source of the Brønsted acidity is the carboxylate layers TiO2 chemisorbs from the air. The investigation of the simultaneous polyolefin hydrocracking and hydrogenolysis on a metal-acid bifunctional catalyst enhances our understanding of the depolymerization chemistry, and guides decisions in process development. The unexpected Brønsted acidity on TiO2-A-SG revealed in this work also carries significant potentials in other acid-catalyzed reactions.