Abstract: Plasticization and modification of the inner and outer part of bamboo were carried out with NaOH solution as swelling agents and catalysts, and benzyl chloride as etherification agent. The molecular structure, micro morphology and surface free energy of the benzylated bamboo were studied and characterized by Furier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and GC contact angle measurement. The results showed that: the molecular structure of modified bamboo varied significantly on FTIR spectrum; the surface morphology had many differences from unmodified bamboo on SEM photograph, the original linear structure disappeared, the surface morphology was more similar to the heated shrinkage plastic; total surface free energy decreased and the polarity part of free energy reduced to half as compared with that of raw bamboo, nonpolarity part of free energy was similar to that of PP plastic, there had excellent interfacial compatibility between benzylated bamboo and plastic. Furthermore, the benzylated bamboo presented selfbonding properties and tended to thermoplasticity.