This report describes a comparative study of dye degradation under 20-watt LED light using the perovskite photocatalyst Calcium Copper Titanate (CCTO) and its compositions (CaxCu3−xTi4O12) (x = 1, 1.5 and 2), synthesized by changing molar ratios of Ca2+ and Cu2+ ions. The 99.74% degradation of Rhodamine Blue (RhB) with composition (x = 1) within 6 h is reflected its better photocatalytic activity than the parent CCTO and other compositions. The band gap energy of the materials 2.18 eV (CCTO), 1.93 eV (x = 1), 2.40 eV (x = 1.5), and 2.55 eV (x = 2) are analysed with UV-Vis spectroscopy. The presences of Ca, Cu, Ti and O in the synthesized photocatalysts are confirmed with Elemental X-ray Dispersive (EDX) analysis. The cubic phases in the polyhedral shape of the materials are detected in X-ray diffraction and Scanning Electron Microscopy (SEM). This report further observes the defect density concentrations of the materials with Photoluminescence Spectroscopy (PL) and provides the approximate explanation of their dye degradation performance as photocatalysts. The rate constants are found in a first order reaction trend; where the composition (x = 1) shows about 1.683×10− 2 min− 1. The mechanistic understanding of the degradation process is also revisited and rationalized with different scavengers for the process.