Herein we present an innovative route for model biomass compounds upgrading via “H2-free” hydrodeoxygenation (HDO) reactions. The underlaying idea is to implement a multifunctional catalyst able to activate water and subsequently use in-situ generated hydrogen for the HDO process. In this sense we have developed a series of effective Ni and Pt based catalysts supported on N-promoted graphene decorated with ceria. The catalyst reached commendable conversion levels and selectivity to mono-oxygenated compounds considering the very challenging reaction conditions. Pt outperforms Ni when the samples are tested as-prepared. However, Ni performance is remarkably boosted upon applying a pre-conditioning reductive treatment. Indeed, our NiCeO2/GOr-N present the best activity/selectivity balance and it is deemed as a promising catalyst to conduct the H2-free HDO reaction. Overall, this “proof-concept” showcases an economically appealing route for bio-compounds upgrading evidencing the key role of advanced catalysts for a low carbon future.