Catalytic hydrogenolysis of polyethylene to liquid alkanes has drawn particular attention. However, it remains not very clear about the factors influencing the positions (internal C secondary À C secondary and terminal C secondary À C primary bonds) of CÀ C bond cleavage. Here, we clarify the influence of Ru chemical state on the positions of CÀ C bond cleavage by designing two Ru/CeO 2 catalysts with different Ru chemical states tuned by the metal-support interaction. It is found that the positively charged Ru species favor the hydrogenolysis of the internal C secondary À C secondary bond, inhibiting methane production, because these Ru δ + species enable the selective bonding with the internal C secondary containing higher electron density through the electron-donating effect of adjacent alkyl species instead of the terminal C primary . Furthermore, a simple Ru/CeO 2 À I catalyst with plenty of Ru δ + species was designed and was efficient for the hydrogenolysis of real waste polyethylene plastics. This work would guide catalyst design to enhance the selective production of liquid alkanes.