Ferrocene-bridged polysilsesquioxanes film electrodes were prepared via depositing the sols formed by hydrolysis of 1,1'-bis[(2-triethoxylsilyl)ethyl]ferrocene (BTEF) or co-hydrolysis of poly(vinylalcohol) (PVA) with BTEF or tetraethoxysilane (TEOS) with BTEF onto glassy carbon electrode (GCE) surface. The electrochemical behavior of the modified electrodes were characterized by cyclic voltammogram (CV) in aqueous solution. The BTEF film, BTEF/PVA film and BTEF/TEOS film all exhibit a redox wave at E-0' are 0.504, 0.326, 0.318 V, with the peak potential separation (Delta E) are 0.132, 0.042, 0.028 V, and the value of i(pa)/i(pc) are 1.8097, 1.007, 1.064 (vs. SCE), respectively. This suggests that BTEF/PVA film and BTEF/TEOS film have a good reversible redox behavior and the redox peak is corresponded to a one-electron reduction and oxidation process. After successive 50 time's cyclic voltammetric, there is no peak potential shift, and the peak current only decreased 5.58, 4.95%, respectively. BTEF/PVA film has better hydrophilicity and shows a more perfect electrocatalytic activity in the oxidation of H(2)A than that of the BTEF/TEOS film. The catalytic peak current has a linear relationship with the concentration of H(2)A in the range of 1.0 x 10(-5)similar to 1.0 x 10(-3) M.