A solar Fenton process was applied as post-treatment to selectively eliminate organic pollutants and toxicants in bleaching effluents of kraft pulp mills. Experiments were conducted to study the effect of system parameters (pH, initial concentration of H2O2, molar ratio of Fe2+/H2O2 and solar-UV irradiance) on the removals of chemical oxygen demand and colour. The results showed 92.8% of COD and 99.6% of colour were removed at pH 3.5, H2O2 30 mM/ L, Fe2+/H2O2 1:100, solar-UV irradiance 11070 mW/m2, reaction time 120 min. The first-order kinetic model was used to study the dependence of the reaction rate on solar-UV irradiance: a linear relationship was shown to exist between reaction rate constants and solar-UV irradiance. The results of gas chromatography mass spectrometry analysis showed that the toxicity of the bleaching effluents was mainly derived from the presence of mononuclear aromatics, polycyclic aromatic hydrocarbons and organochlorides, which were all degraded into harmless organic acids under the attack of hydroxyl radicals generated from the solar Fenton reaction.