Ca2+-containing porous gelatin-siloxane hybrids were prepared using sol-gel process, post-gelation soaking, and freeze-drying. The porosity and pore size of the hybrids could be well controlled by the freezing temperature and the pH value of the soaking solution. The pore characteristics were related to the structure change during the soaking treatment. A bone-like apatite layer was able to form in the Ca2+-containing porous gelatin-siloxane hybrids upon soaking in a stimulated body fluid. The porous gelatin-siloxane hybrids could release gentamicin sulfate which is an antibiotic drug in bone chemotherapy. Thus, those hybrid materials are proposed to find application as novel bioactive and biodegradable scaffolds in bone tissue engineering.