Zero-valent iron (ZVI) pre-treatment in sequential strategy for removal of non-biodegradable azo-dye Orange II by activated-sludge was quantitatively examined. The decolorization and TOC (total organic carbon) removal of Orange II by ZVI pre-treatment were examined in the ranges of pH from 3 to 11 and ZVI dosage from 500 to 2000 mgL. While the decolorization was enhanced with decreasing pH and the optimal pH for decolorization was found at pH 3, the TOC removal rate at pH 3 remained at 22.2% and the maximum TOC removal rate of 78.2% was obtained at pH 4. The decolorization and TOC removal of Orange II were monotonously increased with increasing ZVI dosage. To quantify the ZVI pre-treatment, the contributions of redox degradation, complexation/precipitation and adsorption to TOC removal by ZVI were defined. Novel kinetic models for the ZVI pre-treatment and activated-sludge post-treatment were developed. The proposed kinetic models satisfactorily predicted the transitional behaviors of the ZVI pre-treatment and activated-sludge post-treatment and the contributions of redox degradation, complexation/precipitation and adsorption to TOC removal by the ZVI pre-treatment. The complete removal of non-biodegradable azo-dye Orange II of 300 mgL was accomplished by 78.2% removal after 360 min ZVI pre-treatment with the ZVI dosage of 1000 mgL at pH 4 and subsequently 21.8% removal after 480 min activated-sludge post-treatment. The ZVI pre-treatment integrated with activated-sludge post-treatment was proved to be an effective strategy for treating non-biodegradable pollutants.