Background: Filamentous fungi have the ability to efficiently decompose plant biomass, and thus are widely used in the biofuel and bioprocess industries. In process, ambient pH has been reported to strongly affect the performance of the applied functional filamentous fungi. In this study, Trichoderma guizhouense NJAU4742 was investigated under the fermentation of rice straw at different initial pH values for a detailed study. Results: The results showed that NJAU4742 strain could tolerate ambient pH values ranging from 3.0 to 9.0, but had significantly higher growth speed and extracellular enzyme activities under acidic conditions. At low ambient pH (< 4), NJAU4742 strain achieved rapid degradation of rice straw by elevating the ambient pH to an optimal range through environmental alkalinization. Further proteomic analysis identified a total of 1139 intracellular and extracellular proteins during the solid-state fermentation processes, including the quantified 190 carbohydrate-active enzymes (CAZymes) responsible for rice straw degradation, such as 19 cellulases, 47 hemicellulases and 11 chitinases. Meanwhile, the analysis results clearly showed that the secreted lignocellulases had a synergistic trend in distribution according to the ambient pH, and thus led to a pH-dependent classification of lignocellulases in T. guizhouense NJAU4742. Conclusions: Most functional lignocellulases were found to be differently regulated by the ambient pH in T. guizhouense NJAU4742, which had the ability of speeding up biomass degradation by elevating the ambient pH through environmental alkalinization. These findings contribute to the theoretical basis for the biodegradation of plant biomass by filamentous fungi in the biofuel and bioprocess industries.