Hollow mesoporous hydroxyapatite (HM-HAP) composites coated with titania are prepared to increase the stability and catalytic performance of titania for azo dyes present in the wastewater system. In this work, HM-HAP particles were first synthesized by a hydrothermal method utilizing the CaCO3 core as a template and then coated with titania to form TiO2/HM-HAP composites. Utilizing SEM, XRD, XPS, BET, FTIR, EDS, UV–vis DRS spectroscopy, and point of zero charge (PZC) analysis, the coating morphological and physicochemical parameters of the produced samples were analyzed. The photocatalytic efficiency of the synthesized coated composites was assessed by the degradation of methyl red (MR) dye in water. The results indicated that TiO2/HM-HAP particles could efficiently photodegrade MR dye in water under UV irradiation. The 20% TiO2/HM-HAP coating exhibited high catalytic performance, and the degradation process was followed by the pseudo-first-order (PFO) kinetic model with a rate constant of 0.033. The effect of pH on the degradation process was also evaluated, and the maximum degradation was observed at pH 6. The analysis of degraded MR dye products was investigated using LC-MS and FTIR analysis. Finally, a good support material, HM-HAP for TiO2 coatings, which provides a large number of active adsorption sites and has catalytic degradation performance for MR dye, was revealed.