The aim of this study was to determine the photocatalytic performance of copper-doped TiO2 (Cu-TiO2) specimens on the degradation of dissolved organic matter (DOM) represented by a model humic acid (HA). TiO2 was synthesized by sol-gel method from an alkoxide precursor. Cu-doped TiO2 specimens containing 0.25 wt% and 0.50 wt% Cu were prepared by wet impregnation method using sol-gel synthesized as well as bare TiO2 P-25 and characterized by XRD, SEM, XPS, Raman spectroscopy, UV-DRS, and BET measurements. Their photocatalytic activities were evaluated with regard to degradation kinetics of HA in terms of UV-vis and fluorescence spectroscopic parameters and organic contents. HA fluorescence excitation emission matrix (EEM) contour plots indicated that the solar photocatalytic degradation pathway was TiO2-type specific and Cu dopant content.