Hydroxypropyl guar gum is considered to be a main component of oilfield fracturing wastewater (OFW). This work is intended to optimize the experimental conditions for the maximum oxidative degradation of hydroxypropyl guar gum by the coagulation and UV/H2O2/ferrioxalate complexes process. Optimal reaction conditions were proposed based on the chemical oxygen demand (COD) removal efficiency and UV_vis spectra analysis. The overall removal efficiency of COD reached 83.8% for a dilution ratio of raw wastewater of 1:2, pH of 4 and FeCl3 loading of 1,000 mg/L in the coagulation process; the dosage of H2O2 (30%,v/v) was 0.6% (v/v) and added in three steps, the n(H2O2)/n(Fe2+) was 2:1, n(Fe2+)/n(C2O42−) was 3:1 and pH was 4 in the UV/H2O2/ferrioxalate complexes process; pH was adjusted to 8.5–9 by NaOH and then cationic polyacrylamide (CPAM) of 2 mg/L was added in the neutralization and flocculation process. The decrease in COD during the coagulation process reduced the required H2O2 dosage and improved efficiency in the subsequent UV/H2O2/ferrioxalate complexes process. Furthermore, COD removal efficiency significantly increased by more than 13.4% with the introduction of oxalate compared with UV/Fenton. The UV_vis spectra analysis results indicated that the coagulation and UV/H2O2/ferrioxalate complexes process could efficiently remove the hydroxypropyl guar gum dissolved in OFW. An optimal combination of these parameters produced treated wastewater that met the GB8978-1996 Integrated Wastewater Discharge Standard level III emission standard.