The role of hydrogen peroxide (H2O2) in the electrocoagulation (EC) treatment for removing toxic organic matters in wet-spun acrylic fibers (WAFs) manufacturing effluents was investigated. The addition of H2O2 in the EC resulted in electro-Fenton (EF) treatment, which improved the removal of organic pollutants. Biodegradability of the EF-treated effluents was significantly improved over the EF treatment and reached 0.18. In addition, evaluation of the toxicity of the treated effluents using luminous bacteria revealed that the EF treatment resulted in the greater removal of toxic compounds than the EC treatment, with 80.9% decline in the EC50.