Heterogeneous photocatalytic degradation of γ-HCH on soil surfaces was carried out to evaluate the photocatalytic effectiveness of α-Fe2O3 and TiO2 toward degrading γ-HCH on soil surfaces. After being spiked with γ-HCH, soil samples were loaded with α-Fe2O3 or TiO2 and exposed to UV-light irradiation. Different catalyst loads(0%, 2%, 5%, 7%, and 10% (wt). α-Fe2O3; 0%, 0.5%, 1%, 2% wt. TiO2) were tested for up to 7 d irradiation. The effects of soil thickness, acidity, and humic substances were also investigated. The obtained results indicated that the γ-HCH photodegradation follows the pseudo-first-order kinetics. The addition of α-Fe2O3 or TiO2 accelerates the photodegradation of γ-HCH, while the photodegradation rate decreases when the content of α-Fe2O3 exceeds 7%(wt.). The degradation rate increases with the soil pH value. Humic substances inhibit the photocatalytic degradation of γ-HCH. Pentachlorocyclohexene, tetrachlorocyclohexene, and trichlorobenzene are detected as photodegradation intermediates, which are gradually degraded with the photodegradation evolution.