Uniform core-shell Pd@IRMOF-3 nanostructures, where single Pd nanoparticle core is surrounded by amino-functionalized IRMOF-3 shell, are prepared by a facile mixed solvothermal method. When used as multifunctional catalysts, the Pd@IRMOF-3 nanocomposites exhibit high activity, enhanced selectivity, and excellent stability in the cascade reaction. Both experimental evidence and theoretical calculations reveal that the high catalytic performance of Pd@IRMOF-3 nanocomposites originates from their unique core-shell structures.