The efficacy of anionic surfactant—sodium alkylbenzene sulfonate (ABS) degradation in the river waters and model solutions containing humic acid by various oxidation processes has been compared. The most effective method is photocatalytic ozonation (O3/TiO2/UV) which ensures maximum reduction of ABS concentration (94%-95% over 20–30 min) from ~5 mg/dm3to values not exceeding the MPC (<0.5 mg/dm3) and the highest degree of total organic carbon (TOC) removal (up to 74%) at the lowest values of specific ozone consumption per 1 mg/dm3of TOC compared to ozonation and O3/UV. Photocatalytic oxidation with air oxygen (O2/TiO2/UV) and O3/UV treatment provides a smaller decrease in ABS concentrations (86%–93% and 71%–87% within 20–30 min, resp.) and significantly lowers TOC removal (up to 57% and 47%, resp.). Ozonation and UV irradiation, used separately, are inefficient methods for ABS degradation (<40%), and for TOC removal (<15%).