Methylene blue (MB)/TiO 2 hybrid thin films were prepared on glassy carbon (GC) electrode surface by the liquid phase deposition (LPD) process. The electrochemical measurements indicated that MB retained its electrochemical activity in the hybrid films. The linear dependence of the reduction peak current for MB upon the scan rate and linear relationship between the middle point potential of MB and pH revealed the surface-confined two-proton two-electron electrochemical characteristics of MB entrapped in hybrid LPD films. Although the electron transfer of K 3 [Fe(CN) 6 ] on GC surface was inhibited by TiO 2 film, the catalytic reduction of K 3 [Fe(CN) 6 ] by MB was observed on the MB/TiO 2 hybrid films. The electrocatalytic activity of hybrid films was also demonstrated as an “artificial peroxidase” for the catalytic reduction of H 2 O 2 .