Metal-based catalysts ranging from nanoparticles (NPs) to the atomic level usually exhibit varying catalytic performance. The underlying size effect is both fascinating and evident. This study thoroughly investigates the size-dependent effects of Fe-based catalysts on catalytic transfer hydrogenation (CTH) of furfural (FF) at the atomic level. Fe was precisely loaded onto N-doped porous carbon in three forms: single atoms (Fe-SAs/NC), atomic clusters (Fe-ACs/NC), and nanoparticles (Fe-NPs/NC). This was achieved through meticulous control of the iron precursor composition. Remarkably, Fe-SAs/NC exhibited exceptional catalytic efficiency, achieving an FF conversion of 91.3% and a turnover frequency (TOF) of 262.3 h