Produced water (PW) is the largest waste stream generated by hydraulic fracturing in an unconventional shale gas reservoir. Oxidation processes (OPs) are frequently used as advanced treatment method in highly complicated water matrix treatments. However, the degradation efficiency is the main focus of research, organic compounds and their toxicity have not been properly explored. Here, we obtained the characterization and transformation of dissolved organic matters of PW samples from the first shale gas field of China by two selected OPs using FT-ICR MS. CHO, CHON, CHOS, and CHONS heterocyclic compounds associated with lignins/CRAM-like, aliphatic/proteins, and carbohydrates compounds were the major organic compounds identified. Electrochemical Fe²⁺/HClO oxidation preferentially removed aromatic structures, unsaturated hydrocarbons, and tannin compounds with a double-bond equivalence (DBE) value below 7 to more saturated compounds. Nevertheless, Fe (VI) degradation manifested in CHOS compounds with low DBE values, especially single bond compounds. Oxygen- and Sulfur-containing substances, primarily O_4-11, S₁O₃-S₁O₁₂, N₁S₁O₄, and N₂S₁O₁₀ classes, were the main recalcitrant components in OPs. The toxicity assessment showed that the free-radical-formed Fe²⁺/HClO oxidation could cause significant DNA damage. Therefore, the toxicity response byproducts need spcial attention when conducting OPs. Our results led to discussions on designing appropriate treatment strategies and the development of PW discharge or reuse standards.