2,5-Bis(aminomethyl)furan as a promising monomer was efficiently synthesized in 94.1% yield from biomass-derived 2,5-diformylfuran dioxime. The high selectivity is likely to be a result of the controlled reaction pathway over Rh/HZSM-5, which enhanced the sequence of the dehydration–hydrogenation of 2,5-diformylfuran dioxime owing to the surface acidity on the HZSM-5 support.