We investigated the simultaneous application of peroxymonosulfate (PMS) and electrogenerated H2O2 in presence of ultra violet (UV) to decolorize Acid Brown 14 (AB14). The effects of various operating parameters were evaluated on performance of the hybrid system for decolorization and degradation of AB14. The results showed that the optimal conditions were at UV light intensity of 2.08mW/cm2, pH=4, 200 mA applied current and 3mM PMS. Moreover, presence of transitional metals (Co2+, Fe2+ and Cu2+) increased decolorization of AB14 significantly. Decolorization was promoted from 80.9% to 97% by addition of Fe2+ within 20 min reaction time. First-order model was fitted for this system in absence and presence of Fe2+ with rate constants of 1.937×10^(-3) and 3.595×10^(-3) s-1 respectively. Scavenging experiments confirmed that sulfate and hydroxyl radicals were equally effective in degradation of AB14. This hybrid process increased the average oxidation state (AOS) from 0.2 to 2.3.