Bamboo is highly susceptible to mold infection owing to the presence of large number of holes and rich nutrients, resulting in huge economic losses. Chemical bacteriostasis plays an effective role in mildew prevention, however it has adverse effects on the human body and environment. Nowadays, people are paying considerable attention to green and safe methods of bamboo protection. Glycerol monolaurate and phytol are natural and environmentally-friendly fungicides. In this study, a complex emulsion was prepared using phytol, glycerol monolaurate, and carnauba wax. The preparation process was studied using orthogonal experiments, and the properties of the emulsion were characterized. The emulsifier ratio was found to have a significant effect on the particle size and solid content of the emulsion. The anti-mildew property of emulsion-treated bamboo was also evaluated. The emulsion particles were deposited onto the surface and inside of the bamboo. All the contact angles of the treated bamboo were above 120° and most of the natural stacking occurred after 28 days without mildew. The anti-mildew mechanism of the complex emulsion was to combine the physical barrier of wax with the chemical inhibition of glycerol monolaurate and phytol to prevent mold infection of bamboo. The glycerol monolaurate/phytol and carnauba wax-based complex emulsion is expected to benefit the protection of bamboo products.