Catalytic hydrogenolysis of polyethylene to liquid alkanes has drawn particular attention. However, it remains not very clear about the factors influencing the positions (internal Csecondary−Csecondary and terminal Csecondary−Cprimary bonds) of C−C bond cleavage. Here, we clarify the influence of Ru chemical state on the positions of C−C bond cleavage by designing two Ru/CeO2 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 Csecondary−Csecondary bond, inhibiting methane production, because these Ruδ+ species enable the selective bonding with the internal Csecondary containing higher electron density through the electron‐donating effect of adjacent alkyl species instead of the terminal Cprimary. Furthermore, a simple Ru/CeO2−I catalyst with plenty of Ruδ+ 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. [ABSTRACT FROM AUTHOR]