Livestock wastewater (LWW) has a complex characteristic of high organic matter content, metals, nutrients, and pharmaceutical compounds. Advanced oxidation processes (AOP) are a potential option for treating this wastewater. This study evaluated real LWW and the performance of UV/H2O2 and UV/peroxymonosulfate (UV/PMS) for its treatment. The experiments were conducted in a UV photoreactor (16 mW/m2, λ = 254 nm). The oxidant agents (Ox) tested were H2O2 and PMS, each at low, medium, and high TOC/Ox molar ratios. A pretreatment based on chemical precipitation was implemented. Annually, the LWW showed total organic carbon (TOC) values of 859 ± 13.37 mg/L, 168.85 ± 1.62 mg/L of total Kjeldahl nitrogen (TKN), and toxicity of 96% v/v. In the dry season, albendazole (ABZ) (95.3 ± 35.16 mg/L), Cu (4.3 ± 0.23 mg/L), Fe (3.8 ± 0.38 mg/L), and suspended solids (SS) (1015 ± 586.9 mg/L) were identified, so pretreatment was implemented. The UV/PMS process with the lowest molar ratio [TOC/Ox 1:0.75] removed significantly lower TOC concentrations (p < 0.05), but toxicity decreased entirely. The study of mineralization and toxicity provided insight into the changes in LWW during treatment with AOP. Furthermore, it contributed to establishing the technical basis for implementing efficient treatment processes.