The surface of plant fibers was modified by silane coupling agents to prepare plant fiber/polylactic acid (PLA) composites, which can improve the dispersion, adhesion, and compatibility between the plant fibers and the PLA matrix. In this work, three silane coupling agents (KH550, KH560, and KH570) with different molecular structures were used to modify the surface of waste corrugated paper fibers (WFs), and dichloromethane was used as the solvent to prepare the WF/PLA composites. The effects of different silane coupling agents on the microstructure, mechanical properties, thermal decomposition, and crystallization properties of the composites were studied. The mechanical properties of the composites treated with 4 wt% KH560 were the best. Silane coupling agents can slightly improve the melting temperature of the composites, and WFs can promote the crystallization of PLA. The modification of WFs by silane coupling agents can increase the decomposition temperature of the WF/PLA composites. The content and type of silane coupling agent directly affected the mechanical properties of the WF/PLA composites. The interfacial compatibility between the WFs and PLA can be improved by using a silane coupling agent, which can further enhance the mechanical properties of WF/PLA composites. This provides a research basis for the further improvement of the performance of plant fiber/PLA composites.