Luminescent Mn/Co/Ti LDH, synthesized by a single step hydrothermal route, has been found to be optically responsive for utilization as a highly efficient photocatalyst in destruction of the cationic dye Rhodamine B, in aqueous solution under visible light irradiation. The material has been found to be better than the commercial catalysts like MnO, CoO, TiO2 and Degussa P25. Multiple techniques like XRD, XPS, FT-IR, EIS, TG, UV-visible DRS, PL, TRES, N2-sorption-desorption, dynamic light scattering, TEM-EDS and AFM analyses were used to characterize the LDH. The results indicated Mn/Co/Ti LDH to have a multilayered crystalline structure with hexagonal morphology that carries metal ions in mixed valences, oxygen vacancies, defect states, thermal stability, narrow band gap, high surface area, and electrostatic surface charge variation with pH. The photocatalytic activity of the LDH could be co-related with the structural aspects such as oxidation states, narrow band gap, high surface area and existence of defects. The active species responsible for photocatalysis have been evaluated with EPR, terephthalic acid fluorescence probe and indirect radical-hole trapping experiments. The photodegradation mechanism involves electron and hole hopping across the material and also photosensitization of the dye. Ex situ 1H-NMR and GC-MS analyses of the colorless end products of Rhodamine B destruction provide further insight into the reaction mechanism. The complete mineralization of the decolorized end product of degradation was evaluated with TOC analysis. The results indicate the potential for using multi metal incorporated LDH in destroying dyes and their degradation products in industrial wastewater.