The present study involves a novel protocol to develop a ternary composite catalyst for an effective post-treatment technique for greywater. The ternary film of Fe2O3–TiO2/polyvinyl pyrrolidine (PVP) is coated on a glass tube using spray coating with annealing at 320 °C. The structure, thermal, microstructure, and surface properties of the coated film are characterized by X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Field Emission Scanning Electron Microscopy (FESEM), and Thermo Gravimetric Analysis (TGA). The scratch hardness of photocatalysts at different Fe2O3/TiO2 compositions is investigated based on the width measurement of scratch using FESEM analysis. Results show that at an optimum coating of 5% of Fe2O3/TiO2 composition catalytic film, the maximum scratch hardness (7.984 GPa) is obtained. Also, the photocatalyst has the highest cohesive bond strength and wearing resistance. The degradation of triclosan (TCS) in treated greywater, discharged from the anaerobic-aerobic treatment system, is investigated at a lab-scale using a solar photocatalytic reactor. The response surface analysis has been performed from the different sets of experimental trials for various optimal parameters. It is observed that the TCS degradation efficiency of 83.27% has resulted under optimum conditions.