Dissolved organic matter plays an important role in pollution migration from human waste to aquatic environments. In this study, the effect of humic acid (HA) on the photo-chemical transformation of naphthalene by irradiation model solar and UV light was reported using fluorescence quenching titrations. It was calculated the interactions between naphthalene and humic acids. It is found that the molecular complex of humic acid and naphthalene is more stable to UV irradiation, compared with the model solar radiation. The application of molecular fluorescence spectrometry is a useful sensitive tool evaluate intermolecular HA and naphthalene interactions.