A bimetallic nanocatalyst with unique surface configuration displays extraordinary performance for converting biomass-derived polyols to chemicals, with potentially much broader applications in the design of novel catalysts for several reactions of industrial relevance. The synthesis of nanostructured metal catalysts containing a large population of active surface facets is critical to achieve high activity and selectivity in catalytic reactions. Here, we describe a new strategy for synthesizing copper-based nanocatalysts on reduced graphene oxide support in which the catalytically active {111} facet is achieved as the dominant surface by lattice-match engineering. This method yields highly active Cu-graphene catalysts (turnover frequency = 33-114 mol/g atom Cu/h) for converting biopolyols (glycerol, xylitol, and sorbitol) to value-added chemicals, such as lactic acid and other useful co-products consisting of diols and linear alcohols. Palladium incorporation in the Cu-graphene system in trace amounts results in a tandem synergistic system in which the hydrogen generated in situ from polyols is used for sequential hydrogenolysis of the feedstock itself. Furthermore, the Pd addition remarkably enhances the overall stability of the nanocatalysts. The insights gained from this synthetic methodology open new vistas for exploiting graphene-based supports to develop novel and improved metal-based catalysts for a variety of heterogeneous catalytic reactions.