The enhancement of the physical and mechanical properties and the anti-mildew performance of wood–plastic composites are of great significance for broadening their application field. In this research, bamboo fibers underwent treatments with safe, environmentally friendly bio-enzymes. Subsequently, a bamboo–plastic composite (BPC) was developed using the modified bamboo fibers and polyethylene. The effects of biological enzymatic treatments on the surface free energy, the chemical composition of the bamboo fibers, water resistance, thermal stability, bending performance, impact performance, and anti-mildew performance of the BPC samples were analyzed. This study revealed that treating bamboo powder with bio-enzymes (xylanase, lipase, laccase, pectinase, hemicellulase, or amylase) decreased the surface free energy and the polar components of the bamboo fibers while improving the surface O/C atomic ratio of the bamboo fibers. These enzyme treatments enhanced the water resistance, bending performance, and anti-mildew performance of the BPC samples. However, on the whole, the thermal stability of the composites decreased. Particularly, after hemicellulase treatment, the composites had the lowest water absorption, reflecting a decrease of 68.25% compared to the control group. With xylanase modification, the 24 h water absorption thickness swelling rate of the composites was the lowest, reflecting a decrease of 71.27% compared to the control group. After pectinase modification, the static bending strength and elastic modulus of the prepared composites were the highest, with an increase of 15.45% and 13.31%, respectively, compared to the unmodified group. After xylanase modification, the composites exhibited the best anti-mildew effect, with an anti-mold effectiveness of 74.67%. In conclusion, bio-enzyme treatments can enhance the physical and mechanical properties and anti-mildew performance of BPCs. This research provides a theoretical foundation for the preparation of high-performance wood–plastic composites.