Bamboo fibers (BFs)-reinforced epoxy resin (EP) composites are prepared by resin transfer molding (RTM). The influence of BFs surface modification (NaOH solution or coupling agents, i.e., KH550 and KH560) on interfacial properties of BFs/EP composites is systematically investigated. The synergistic effect of hydrolysis, peeling reaction of BFs, and the condensation reaction of hydrolyzed coupling agents are confirmed by FTIR. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) reveal that the interfacial compatibility of NaOH- and silane-modified BFs/EP composites was significantly improved. KH550-modified BFs/EP composite renders optimal tensile, flexural, and impact strength values of 68 MPa, 86 MPa, and 226 J/m. The impact resistance mechanism at the interface of BFs/EP composites was proposed. Moreover, the dynamic mechanical properties, creep behavior, and differential scanning calorimetry of BFs/EP composites have also been carried out to understand thermal stabilities. Overall, the surface-modified BFs-reinforced EP composites exhibited superior interfacial bonding.