The replacement of fossil resources with biomass resources in the construction of N-heterocycles is rapidly attracting research interest. Herein, we report palladium-catalyzed selective hydrogenative coupling of nitroarenes and phenols based on a transfer hydrogenation strategy, allowing straightforward access to spirocyclic pyrrolo- and indolo-fused quinoxalines, a class of compounds found in numerous natural alkaloids. The synthetic protocol is characterized by a broad substrate scope and the utilization of biomass-derived reactants and commercially available catalysts. In such transformations, high-pressure and explosive hydrogen are not required. This report provides a new protocol for converting biomass-derived phenols into value-added nitrogen-containing chemicals.