The sustainable production of carbamates from biomass-derived molecules provides a viable alternative to petrochemical-based production routes. In this work, we reported an efficient catalytic strategy for synthesizing bio-based furfurylmethyl carbamate (FMC) through methoxycarbonylation of furfurylamine with dimethyl carbonate (DMC) under mild conditions. A novel Pb–Ni composite oxide catalyst with high activity and stability was developed, which significantly outperformed conventional monometallic oxide catalysts. Comprehensive characterization revealed that the synergistic interaction between Pb and Ni species constructed composite oxide nanoparticles (about 11.4 nm), with Pb species highly dispersed on the NiO matrix. Consequently, highly defective structure, abundant acid–base dual sites, and a high specific surface area were concurrently formed, which were identified as critical factors for activating both nucleophilic and electrophilic reactants. Significantly, appreciable quantities of furfuryl isocyanate (FIC) were detected, demonstrating the feasibility of a one-pot cascade synthesis of bio-based isocyanates from amines and DMC.