After anaerobic-oxic (A/O) treatment, there are often high chromaticity levels in piggery bio-treatment effluents, which still contain a high concentration of refractory organics. This paper describes the use of piggery biogas residue biochar (BioC) to support MnO2 to prepare a catalyst (MnO2/BioC) and examines the effects of catalyst addition, pH and ozone dosage on chromaticity and organic matter degradation in the ozonation process. Three-dimensional fluorescence spectroscopy (3D-EEM) and GC-MS were used to analyse changes in the organic component of the effluent before and after ozonation. The results indicate that the decolorization percentages reached 91.29% and that the UV254 and CODcr removal percentages reached 81.64% and 61.07%, respectively, when the MnO2/BioC catalyst addition amount was 1.0 g·L-1, the pH was 9.0, and the ozone dosage was 0.45 g·L-1. The 3D-EEM analysis results showed that the macromolecular organics mainly consisted of humic acids before treatment, and the removal of humic acid organic matter after treatment had an obvious effect. The GC-MS analysis results showed that the refractory organics were mainly phenols, esters, alcohols and hydrocarbons, and most of the refractory organics were oxidatively degraded after treatment. These results show that ozone catalytic oxidation treatment of piggery bio-treatment effluent can reduce chromaticity and refractory organics.