In the present work, an effort was made for the first time to develop novel catalysts by recycling broken borosilicate glass (BSG) loaded with iron and cobalt for the abatement of methylene blue (MB) and COD from real textile wastewater. In the study, the comparison of adsorption, single ozonation (SO), and catalytic ozonation with both catalysts (Fe-BSG) and (Co-BSG) for the removal of MB was evaluated on various operational parameters such as ozone flow (0.552–1.08 mg/min), reaction time (2–23 min), catalyst dose (1.25–5 g/L), and pH (4–10). Moreover, the prepared catalysts Fe-BSG and Co-BSG were characterized by SEM, FTIR, EDS, and BET. Furthermore, results revealed that the Co-BSG/O3 was more efficient than others and decolorization of MB was found to be 6.2%, 72%, 79%, and 92% at 6.8 pH in 8 min, and removal of COD was 3.5%, 69%, 81%, and 93% at pH 6.8 in 40 min for BSG, SO, Fe-BSG/O3, and Co-BSG/O3, respectively. In the current investigation, the tert-butyl alcohol effect exposed the leading role of hydroxyl radicals during Co-BSG/O3 as the MB efficiency was reduced by 28% in addition of hydroxyl radical scavengers as compared to the SO process. It was found that the catalyst remained stable and efficient after 3 cycles due to the minute quantity of metal leached. Therefore, the studied novel advanced method may significantly be applied on the industrial scale for the abatement of dyes and COD from real textile wastewater.