A series of pincer ((PCP)-P-tBu)Pd(II)-OR complexes ((PCP)-P-tBu = 2,6-bis((CH2PBu2)-Bu-t)C6H3, R = H, CH3, C6H5, CH2C(CH3)(3), CH2CH2F, CH2CHF2, CH2CF3) were synthesized to explore the generality of hydrogenolysis reactions of palladium-oxygen bonds. Hydrogenolysis of the Pd hydroxide complex to generate the Pd hydride complex and water was shown to be inhibited by formation of a water-bridged, hydrogen-bonded Pd(II) hydroxide dimer. The Pd alkoxide and aryloxide complexes exhibited more diverse reactivity., Depending on the characteristics Of the -OR ligand (steric bulk, electron donating ability, and/or the presence of beta-hydrogen atoms), hydrogenolysis was complicated by hydrolysis by adventitious water; a lack of reactivity with hydrogen, or a competing dissociative beta-hydride abstraction reaction pathway. Full selectivity for hydrogenolysis.:was observed with the Partially fluorinated Pd(II) 2-fluoroethoxide complex. The wide range of Pd-OR substrates examined helps to clarify the Variety of reaction pathways available to late-transition-metal alkoxides as well as the conditions necessary to tune the reactivity to hydrogenolysis, hydrolysis, or dissociative beta-hydride abstraction.