Biomass-derived 5-hydroxymethylfurfural (HMF) holds potential for applications in green materials, but its conventional synthesis is hindered by undesired side reactions. This study presents a catalytic system that effectively suppresses the formation of byproducts, thus enhancing HMF yield. The system demonstrated synergistic effects between Lewis acid NaY zeolite and formic acid sacrificial agent for the production of HMF from glucose. The results indicate that formic acid reacts with reactive intermediates from glucose decomposition, preventing their interactions with other sugar-derived species in the dehydration path to HMF. Such effect originates from the neutral formic acid species rather than the dissociated acidic proton normally observed in Brønsted acid-catalyzed reactions. The NaY/formic acid catalysts in isopropanol/water achieved a 57% HMF yield, a significant improvement over 31% and 27% yields with NaY or formic acid alone, respectively. Moreover, performance of the spent catalysts was easily restored to the original state via a simple NaCl wash.