Iron and arsenic have been found to coexist in a water environment and the fate of arsenite in the aquatic system is influenced by iron. Goethite is a form of iron hydroxide, which is commonly found in sediments. In previous studies, we have used iron complexes to degrade organic pollutants. Results have shown that some organic pollutants could be totally degraded by iron complexes and our work indicated that iron might cause conversion of arsenic when irradiated. This work attempts to investigate the conversion of arsenite [As(III)] using natural goethite, as the iron source, to quantify the effect of various factors on photooxidation. We also consider the possible mechanism for photooxidation of As(III) using a suspension of natural goethite. The As(III) concentration variation under illumination was compared with the one in the dark to quantify the contribution of light to As(III) oxidation to As(V) in goethite suspended solution. The experiments under N(2) and air atmosphere confirmed the participation of dissolved oxygen. The photooxidation efficiency of As(III) under different conditions was compared to determine the effect of different environmental factors such as pH value, goethite concentration, and humic acid concentration on the photooxidation reaction. In the solution containing 100 μg L(-1) arsenite and 0.1 g L(-1) suspended goethite at pH 3.0, nearly 80 % of As(III) was photooxidized after irradiation by a 250-W metal halogen lamp (λ ≥ 313 nm) after 6 h. The effects of initial pH and goethite concentration and humic acid concentration were all examined. The results show that the greatest efficiency of photooxidation of As(III) was at pH 3.0. The extent of photooxidation decreased with increasing goethite concentration and fell sharply in the presence of humic acid under the conditions in this work. Although about 80 % of As(III) was photooxidized after irradiation by a 250-W halogen lamp at pH 3.0 in the presence of goethite suspension, photooxidation was also affected by factors such as pH, concentration of goethite, and presence of humic acid. The scavenger experiments showed that the HO• radical and photogenerated hole are the predominant oxidants in this system responsible for 87.1 % oxidation of As(III), while HO (2)(•) /O(2)(•-) is responsible for 12.9 % oxidation of As(III).