Lead oxides (PbO) of same chemical composition, but different crystallographic properties have been developed for complementary catalytic ozonation (designated by [PbO]_a) and adsorption (designated by [PbO]_b) of a model dye, reactive red–120 (RR-120) with highest possible efficiency beyond the state-of-the-art of individual processes. The highest extent of decolouration (~99% after 4 min) with k^RR-120_app 1.77×10^-2 s^-1 and mineralization (50% after 15 min) of RR-120 at pH 10.5 was achieved by ozonation using 0.5 g/L catalyst [PbO]_a consisting major fraction of α-PbO phase (α-PbO: β-PbO∼4:1) in its crystal structure. Minimum adsorption of RR-120 (∼7%) on catalyst’s surface [PbO]a led to higher accessibility of O₃ to free catalyst surface sites and helped to achieve highest efficiency of catalytic ozonation. On the other hand, adsorbent [PbO]_b mainly consisting of β-PbO phase (α-PbO: β-PbO~1:4) with a fractional coexistence of α-PbO phase showed excellent adsorption of RR-120 (571 mg/g at 320 K) at pH 7.5, but it showed inferior efficiency in catalytic ozonation. Both the materials were found to be reusable and environmentally acceptable.