Abstract Background Agricultural practices that enhance organic matter content in soil can play a central role in sequestering soil organic carbon (SOC) and reducing greenhouse gases emissions. Methods We used a water-soluble iron-porphyrin to catalyze directly in situ oxidative polymerization of soil organic matter in the presence of H2O2 oxidant, with the aim to enhance OC stabilization, and, consequently, reduce CO2 emissions from soil. The occurred SOC stabilization was assessed by monitoring soil aggregate stability, OC distribution in water-soluble aggregates, soil respiration, and extraction yields of humic and fulvic acids. Results Soil treatment with H2O2 and iron-porphyrin increased the physical stability of water-stable soil aggregates and the total OC content in small aggregates, thereby suggesting that the catalyzed oxidative polymerization increased OC in soil and induced a soil physical improvement. The significant reduction of CO2 respired by the catalyst- and H2O2-treated soil indicated an enhanced resistance of polymerized SOC to microbial mineralization. The catalyzed oxidative polymerization of SOC also significantly decreased the extraction yields of humic and fulvic acids from soil. Conclusions The oxidative catalytic technology described here may become an efficient agricultural practice for OC sequestration in soils and contribute to mitigate global changes. Graphical abstract Catalyzed polymerization of soil organic matter.