Lignocellulase production from straw fermentation has been widely investigated but the research has neglected to quantify fermentation-derived residue transformation to the humus-like substance (HULIS). To investigate the conversion efficacy of corn stalk residue to HULIS, the amount of HULIS associated with chemical composition and structural changes of humic acid-like substances (HAL) was investigated in a 30 L solid-state fermentation tank during a short period of eight days. The results show that the highest decomposition rate of corn stalk and the highest activity of cellulase, xylanase, and β-glucosidase appeared at the fourth day. At the end of fermenting process, the amount of humic acid-like substances (HAL) and the percentage of HAL in humus acid (PQ value) increased 17.5% and 8.9%, respectively, indicating Trichoderma reesei facilitates the transformation of corn stalk residue to HAL. Fatty acids decreased while aromatic carbon and carboxyl content significantly increased during the ongoing fermentation, which had a positive impact on the HAL thermal stability. The FTIR spectral and thermal analysis revealed an improvement in HAL degrees of condensation, oxidation, and aromatization. The present study suggests that the residue of corn stalks fermented with T. reesei might be a good fertilizer to improve soil characteristics.