This work proposes the combined sol–gel/solvothermal synthesis method to prepare Cu-doped TiO2 and Fe-doped TiO2 microstructures, and further study their photocatalytic activity in the degradation of Eriochrome Black T (EBT) at neutral conditions using a simulated sunlight source. TiO2:at%M (at%=0.25, 0.5, and 1.0; M = Cu or Fe) catalysts were characterized by X-ray diffractometry, Scanning electron microscopy, Diffuse reflectance UV–Vis spectroscopy, Raman spectroscopy, and Brunauer-Emmett-Teller surface area analysis. All synthesized catalysts showed TiO2 anatase phase with spherical morphology and average particle size of 4 to 8 μm. Transition metal doping did not modify the TiO2 anatase phase. TiO2:at%M catalysts exhibited lower bandgap energies than pure TiO2. TiO2:0.5at%Fe showed the lowest bandgap energy (2.87 eV). TiO2 catalysts with a transition metal content of 0.25at% showed a higher surface area compared to the rest of dopant concentrations. The inclusion of the metallic elements in the TiO2 structure enhances the photocatalytic efficiency of the TiO2 anatase under visible light. TiO2:0.25at%Cu showed the highest EBT degradation yields of 90% color removal, 61% total organic carbon (TOC) reduction, and 87% chemical oxygen demand decrease at 180 min. TiO2:0.25at%Cu and TiO2:0.50at%Fe microspheres retained good degradation efficiency for color and TOC removals even after being reused for three cycles.