A new adsorption measurement method based on photoelectrochemical oxidation principles has been developed. The method can be used to directly quantify the amount of adsorbates at a TiO2 electrode surface in a sensitive and accurate manner. The adsorption of phthalic acid was studied as a test case. The relationship between the amount of adsorbate at the TiO2 surface and the concentration of phthalic acid in the solution was obtained. The adsorption of phthalic acid on TiO2 surface was shown to follow a Langmuir type adsorption model. For the first time, the adsorption equilibrium constant of an adsorbate at TiO2 surface has been photoelectrochemically measured. The adsorption equilibrium constant of phthalate on TiO2 porous film at pH 4.0, K=4.0ױ04 M-1, was obtained using our method, which was close to that obtained by conventional methods. The effect of solution pH on the amount of adsorbate at TiO2 surface was also investigated. The results indicate the adsorption of phthalic acid is mainly of chemical bonding nature.