The chemical modification of bamboo culm was explored based on in situ construction of polyhydroxyethyl methylacrylate (PHEMA) and polymethyl methylacrylate (PMMA) networks into the cell walls. Scanning electron microscopy revealed that the synthesized polymers distributed in both the cell walls and the lumen with the pits blocked. The dimensional stability was tested under three water soaking-drying and moistening-drying cycles. The swelling efficiency of the treated bamboo was under 8% in three cycles of water soaking and drying cycles and was 4% in moistening-drying cycles. The anti-swelling efficiency was 60.5%, 52.7%, and 46.3%, respectively, in the moistening-drying cycles. Laboratory tests on mold resistance showed that no mycelium formed on the treated bamboo, while the untreated control was 100% covered by mold fungi.