The study investigates the influence of process parameters on the effectiveness of ozonation in the removal of organic micro-pollutants from wastewater. Primary and secondary municipal wastewater containing phenol was treated. The effect of operating parameters such as initial pH, ozone dosage, and initial contaminant concentration was studied. An increase in contaminant decomposition with pH (3–11) was observed. The contaminant removal efficiencies increased with an increase in ozone dose rate (5.5–36.17 mg L−1 min−1). Furthermore, the ultraviolet absorbance (UV 254 nm) of the wastewater decreased during ozonation indicating the breakdown of complex organic compounds into low molecular weight organics. Along the reaction, the pH of wastewater decreased from 11 to around 8.5 due to the formation of intermediate acidic species. Moreover, the biodegradability of wastewaters, measured as biological and chemical oxygen demand (BOD5/COD), increased from 0.22 to 0.53. High ozone utilization efficiencies of up to 95% were attained thereby increasing the process efficiency; and they were dependent on the ozone dosage and pH of solution. Ozonation of secondary wastewater attained the South African water standards in terms of COD required for wastewater discharge and dissolved organic carbon in drinking water and increased significantly the biodegradability of primary wastewater.