V2O5-TiO2 binary oxide catalysts were successfully prepared with different wt% V2O5 loading by solid state mechanical mixing (SSDMMix), and these nanocomposites were modified with hexadecyltrimethylammonium bromide (HTAB) and cetyl trimethylammonium bromide (CTAB) and polyvinyl alcohol (PVA) as surfactant. The resulting catalysts were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), Braun-Emmet-Teller (BET) analysis of surface area techniques. The photocatalytic activities of all samples were evaluated by degradation of 4-chlorophenol (4CP) in aqueous solution under UV irradiation. 50 wt% V2O5-TiO2 photocatalyst exhibited much higher photocatalytic activity than pure V2O5, TiO2 and P-25. The interaction between V2O5 and TiO2 affected the photocatalytic efficiency of binary oxide catalysts. In addition, CTAB and HTABassisted samples significantly enhanced the efficiency of 50V(2)O(5)-TiO2 binary oxide catalyst. The highest percentage of 4-chlorophenol degradation (100%) and highest reaction rate (1.69mg L-1 min(-1)) were obtained in 30 minutes with (50V(2)O(5)-TiO2)-CTAB catalyst. It is concluded that the addition of surfactant to binary oxide remarkably enhanced the photocatalytic activity by modifying the optical and electronic properties of V2O5 and TiO2.