Changes in the molecular and structural characteristics of humic acid (HA) during photo-Fenton processes were studied. When aqueous solutions at pH 5.0, which contained HA, Fe(III), and H2O2, were irradiated (lambda > 370 nm), the concentrations of total organic carbon (TOC) decreased with increasing irradiation time, indicating that a portion of the HA was mineralized to CO2 during this process. To investigate the changes in molecular and structural characteristics, the HA was reisolated from the reaction mixtures after each period of irradiation. The increased elution volumes required for isolation by gel permeation chromatography indicated that the molecular size of HA decreased as a result of the irradiation. In the FTIR spectra, ether and epoxide functional groups were identified, after irradiation. These products could be formed via radical coupling and/or via peroxy radical addition reactions to the unsaturated groups in the HA, such as vinyl and aromatic groups. Moreover, an analysis of structural fragments in HA by pyrolysis-GC/MS showed that the cinnamic acid moieties (CA) disappeared, as a result of irradiation. In the molecular weight fractionated HA, the majority of the iron species were complexed with the high molecular weight HA fraction, and the CA levels of the high molecular weight fraction were larger than those in the low molecular weight fraction. These results are consistent with residues, as the reactive sites in the photo-Fenton systems. Therefore, the degradation of these sites in the high molecular weight fraction may serve as a factor in decreasing the molecular size of HA.