<p>N,N-Dimethyldodecylamine (DMA12) was used as a pore-forming agent to promote the porosity of low-density ZnTiO₃/ceramic hollow microspheres (ZnTiO₃(<i>n</i>)/CHM, <i>n</i> = volume (mL) of DMA12 in the precursor) synthesised via the sol–gel method. The surface of CHM was coated with a thin layer of ZnTiO₃. The bandgap energies of ZnTiO₃(0)/CHM, ZnTiO₃(1.5)/CHM, ZnTiO₃(2.5)/CHM and ZnTiO₃(4)/CHM were calculated as 3.59, 3.63, 3.65 and 3.60&#xa0;eV, respectively. The porosity of ZnTiO₃(<i>n</i>)/CHM was enhanced by DMA12, increased in the sequence 0, 1.5, 4 and 2.5&#xa0;mL of DMA12. The largest number of hydroxyl radicals were generated in the reaction involving ZnTiO₃(2.5)/CHM. A total of 20.8% of Acid Red 1 was degraded after 30&#xa0;min of irradiation using ZnTiO₃(0)/CHM, while the degradation efficiency of ZnTiO₃(2.5)/CHM was 82.2% at the same time. ZnTiO₃(2.5)/CHM had a constant activity over five reaction cycles, and the degradation efficiencies were 82.2% and 80.8% in the first and the fifth cycles, respectively. The low-density ZnTiO₃(<i>n</i>)/CHM was prepared to facilitate the mixing of the photocatalyst and water, and to ensure a rapid separation of the photocatalyst from water.</p>