For hydrogenolysis over monofunctional Ru catalysts, when PH2 increases, the CH4 selectivity always decreases because the cleavage of terminal C-C bonds involves more dehydrogenated transition states (TS) than that of internal C-C bonds, and the more facile product desorption suppresses sequential C-C bond cleavage that favors CH4 formation, while the (C2 + C3) / C4 value also decreases in all our studies (Figure ). Therefore, the increase in both values at high PH2 cannot be explained by regioselectivity shifts in hydrogenolysis. Instead, it reflects the transition from a low-PH2 regime, in which hydrocracking dominates, to a high-PH2 regime, in which the contribution from hydrogenolysis is significant. This is consistent with the changes in liquid product distribution, from a narrow distribution around C10-12 with yellow color at ≤ 30 bar (Figures 2b and S3f-g), to a wide double distribution around C10-12 and C18 with no color at ≥ 45 bar (Figures and). In the high-PH2 regime, the isomerization level remains at ~60%, which, along with the double liquid distribution, indicates that both pathways have significant contribution to the reaction. The shift in the prevailing pathway with PH2 suggests that the rate of hydrocracking is less sensitive to PH2 than that of hydrogenolysis. As a result, the bifunctional Ru/TiO2-A-SG converts PP much more effectively at low PH2 than most active monofunctional Ru catalysts (223 gPP gRu -1 h -1 at 5 bar, Figure , compared to ~30 gPP gRu -1 h -1 on Ru/CeO2 26 ). Interestingly, when PH2 increases from 15 to 45 bar, the PP conversion remains constant (Figure ) while the hydrogenolysis rate increases (reflected by higher C1 -C3 yields, Figures ), indicating that the rate of hydrocracking decreases as PH2 increases. In hydrocracking, alkanes are dehydrogenated on the metal, resulted alkenes are transported to BAS, isomerized and cracked through C + intermediates, and then transported back to the metal for hydrogenation (Scheme 1). Since TiO2-A-SG does not have shape selectivity effect from micropores (Figure ), the high C4-5 yields in Figures suggest severe secondary cracking before desorption.