Synthetic dyes are persistent pollutants with poor biodegradability. The present study is about the degradation of direct Congo red dye in aqueous media using the Co-60 gamma radiation source. The experimental conditions such as gamma-ray absorbed doses, amount of oxidant (H2O2) and pH conditions were evaluated. The λmax of dye solution was noted as 498 nm, and then, decrease in absorbance and reduction in chemical oxygen demand (COD) were examined. The complete colour removal of dye was observed at 5 kGy, while a significant COD removal was observed at 15 kGy gamma-ray absorbed dose in conjunction with oxidant for 50 mg/L concentration. It was found that pH has no influence on degradation efficiency. A possible degradation pathway was proposed. The radiolytic end products were monitored by Fourier transform infrared (FTIR) and gas chromatography coupled with mass spectrometry (GC-MS) to explore the degradation mechanism. It was imperative to study the oxidative degradation pathway to provide directions for potential applicability of advanced oxidation process (AOP) in industrial wastewater treatment.