Cobalt-based catalysts having different base strengths were prepared by controlling the amount of yttrium oxide (Y2O3). These catalysts were used for the facile one-pot synthesis of polyetheramine (PEA) from polypropylene glycol (PPG) through reductive amination. It is noticed that high hydrogen partial pressures up to 40 bar inhibit the formation of cobalt nitride and lead to a high PEA yield although it has been known that dehydrogenation from alcohol to ketone is the rate-determining step. The Y2O3-inserted Co-Pd/Molecular sieve13X catalyst also showed high activity toward PEA even at low hydrogen partial pressure. Y2O3 played a crucial role in giving basicity to the catalyst, which not only prevents the formation of cobalt nitride but also promotes hydrogenation of imine to amine at a wide range of H-2 pressure. Thus Y2O3 inserted Co-Pd/Molecular sieve 13X provides unique performance toward enhancing the PEA yield while suppressing the catalyst deactivation caused by the cobalt nitride formation.