The pollution and harm of food waste (FW) are increasingly concerned, which has the dual attributes of pollutants and resources. This study aimed to improve the synthesis efficiency of FW humic substances (HS), and investigating the effect of catechol on the formation mechanism and structure of humic acid (HA) and fulvic acid (FA). Results indicated that catechol incorporation could enable to exhibit higher HS yield and more complex structure, especially the maximum particle size of FA reached 4800 nm. This was due to the combination of catechol with multiple nitrogenous compounds, which accelerated molecular condensation. Spectroscopic scans analysis revealed that Maillard reaction occurs first. Subsequently, Maillard reaction products and amino acids were combined with different sites of catechol, which leads to the difference of molecular structure of HS. The structure of FA is characterized by an abundance of carboxyl and hydroxyl groups, whereas HA is rich in benzene and heterocyclic structures. The structural difference was responsible for the disparity in the functional properties of FA and HA. Specifically, the presence of amino, hydroxyl, pyridine, and carboxyl groups in FA contributes significantly to its chelating activity. This research provides an efficient and sustainable unique solution for the high-value of FW conversion, and provides evidence for understanding the structural evolution of HA and FA.