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Based on the infrared characterization of methyl orange adsorption on TiO2 surface and the titration of TiO2, the triple layer model of methyl orange adsorption on TiO2 was established according to electric double theory. The software FITEQL3.1 was applied to calculate the distribution of organic adsorption on TiO2 surface by introducing dummy components to help to overcome mathematical difficulties. It is shown that the chem. -adsorption species of methyl orange have a great adsorption amount. The adsorption constants of three kinds of surface complexation expressed as SOH+org-,SOH2org2 and SOHorg- are 5.98, 17.57 and -4.2, respectively.