Surface complexation of arsenite (As(III)) on colloidal ferric hydroxide (CFH) plays an important role not only in the adsorptive immobilization of As(III) but also in the subsequent oxidation of As(III) to arsenate (As(V)) through light-induced ligand-to-metal charge transfer (LMCT) in water at near-neutral pH. However, the effects of natural organic matter (NOM), especially humic substances (HSs) and low molecular weight carboxylic acids (CAs), on the photochemistry of the CFH-As(III) system have not been sufficiently understood. In this work, the inhibition of photooxidation of As(III) in terms of the observed apparent rate constant (k_obs) by six HSs (below 16 mg L⁻¹) and seven CAs (below 2.5 mM) has been observed in water containing 66 μM Fe(III) and 5 μM As(III) at pH 7 under simulated solar irradiation consisting of UVA (λ_max 365 nm) and UVB (λ_max 313 nm) lights. Total inhibition factors (T) have been determined from the combined effect of light-screening factor (S) and competitive complexation factor (C), wherein both S and C varied with NOM concentration. S was obtained by determining the absorbance of NOM, and C was obtained by fitting modified Langmuir or Freundlich models to the amount of As(III) desorbed from CFH upon the addition of NOM. Statistical analysis between the experimental T_exp and the calculated one according to T_cal = S × C showed that the Freundlich model (RMSE for HS 0.1609 and for CA 0.1771) was better than the Langmuir model and was statistically robust ($Q_{\text{LOO}}^2$= 0.691 > 0.5). This work provided an estimation method for the effects of NOM on As(III) photooxidation in the presence of CFH as well as a deeper understanding of the transformation of arsenic species in sunlit water.