The reaction of one equivalent of metallocene dichloride Cp2MCl2 (M = Ti, Hf) with two molar equivalents of sodium salt of tri(tert-butoxy)siloxane, (tBuO)3SiONa, in toluene yields Cp2Ti[OSi(OtBu)3]2 (1) and Cp2Hf[OSi(OtBu)3]2 (2). These compounds were characterized by analytical and spectroscopic techniques (C/H/N analysis, FT-IR, NMR, EI-MS, and thermal analysis). An independent thermolysis of 1 and 2 at low temperature resulted in the formation of the corresponding metal silicates MO2.2 SiO2 [M = Ti (3) and Hf (4)] as evidenced by infrared spectroscopy, powder X-ray diffraction analysis (PXRD), and scanning electron microscopy (SEM). These thermally stable amorphous metal silicate materials (3 and 4), albeit exhibiting moderate surface areas, are found to be microporous by N2 adsorption studies. UV-vis-NIR spectroscopy shows low energy band gap Eg = 2.63eV for 3 and 2.99eV for 4 due to the silicon oxide mixed with the corresponding transition metal oxides. The photocatalytic activity of titanium silicate material (3) has been explored in terms of degradation of methylene blue. © 2017 Taylor & Francis Group, LLC.