A simple layered titanate immobilization can significantly enhance the Hb catalytic activity in organic media relative to native Hb, especially in hydrophilic dioxane systems, where the composites have an about 100 times enhancement. The interlayer water should be responsible for the increased nonaqueous catalytic activities of the immobilized Hb due to its strengthened resistance to the distorting of the Hb surface essential water layer by organic solvents.