AbstractMollisol is crucial for solving food security issues, but long‐term excessive application of chemical fertilizers has led to severe Mollisol degradation in Northeast China, especially a rapid decline in soil organic carbon (SOC). In context of the use of crop‐herbage intercropping and straw return as alternatives for some chemical fertilizers, it is important to understand how crop‐herbage intercropping and straw return combined with chemical fertilizers influence labile organic carbon (LOC) fractions that improve SOC. To address this, this study explored how the combined application of maize (Zea mays L.)–Melilotus officinalis intercropping, straw return, and chemical fertilizers affect LOC fractions and mineralized carbon (MC) from the perspective of physical property‐mediated pathways. Thus, a field experiment with six treatments was established in the Songnen Plain of Northeast China: (1) maize monoculture without chemical fertilizers and straw return (CK), (2) maize monoculture with chemical fertilizers and no straw return (CF), (3) maize monoculture with chemical fertilizers and straw return (CFS), (4) maize–M. officinalis intercropping and straw return combined with full application of chemical fertilizers (CFSM), (5) maize–M. officinalis intercropping and straw return combined with half application of chemical fertilizers (1/2CFSM), and (6) maize–M. officinalis intercropping and straw return without chemical fertilizers (SM). The CF and CFS groups had no effect on bulk density and porosity but reduced specific gravity. The CFSM group increased water contents, porosity, LOC fractions, SOC, MC, and CO2 release rate and decreased bulk density and specific gravity. Compared with the CF group, the 1/2CFSM group enhanced water contents, microbial biomass carbon, and water‐soluble organic carbon (WSOC) to 6.36%, 17.91%, and 11.6%, respectively. We found that maize–M. officinalis intercropping, straw return, and reducing chemical fertilizers application improved LOC fractions to increase SOC by positively affecting bulk density, specific gravity, and water contents. Further analysis indicated that WSOC was a key determinant of SOC and maize yields. These findings provide a strategy to increase SOC and rehabilitate degraded soils through crop‐herbage intercropping and straw return combined with reducing chemical fertilizers application, which will contribute to a sustainable and environmentally friendly agriculture.