Chitosan-silicate hybrid membranes were prepared using g-glycidoxy-propyltrimethoxysilane (GPSM) through a sol-gel process. The amino groups of chitosan chains were reacted with the epoxy groups of GPSM and GPSM have a function as the agent to cross-link the chitosan chains. The cross-linking degree of the hybrid membranes was determined by ninhydrin assay. Fourier-transform infrared (FT-IR) spectroscopy and 29Si cross-polarization (CP) magic-angle spinning (MAS)-NMR spectroscopy were used to assess the structure of the hybrid membranes. The biodegradability of the hybrid membranes in phosphate-buffered saline solution or lysozyme solution was investigated as a function of the GPSM concentration.