The employment of single-atom catalysts in the catalytic transfer hydrogenation (CTH) of furfural (FF) to furfuryl alcohol (FAL) has never been effectively explored. Herein, a catalyst of Ni single-atoms supported on nitrogen doped carbon (Ni-SAs/NC) is synthesized and first ever utilized in the CTH of FF to FAL. Atomically dispersed Ni–N4 sites change the electron density at the metal center and exhibit specific adsorption and desorption to FF and FAL, promoting an outstanding catalytic performance with a turnover frequency (TOF) of 832 h−1 and selectivity as high as 97.1% at 130 °C for 2 h. Such performance is 9-fold higher than that of supported Ni nanocatalysts. The Ni-SAs/NC catalyst also exhibits superior stability for the CTH of FF and excellent catalytic activity for other α,β-unsaturated aldehydes. This work provides a new strategy of producing green chemical compounds using catalytic biomass conversion and suggests the future application of long-lasting single-atom catalysts for emerging sustainable technologies.