In this work, CoTiO₃/TiO₂ (CTO/Ti) heterostructures were prepared by a hydrothermal procedure in a neutral medium using perovskite CoTiO₃ and tetraisopropyl titanate. Characteristics of the synthesized catalysts were analyzed by various techniques including X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, UV–vis diffuse reflectance spectroscopy, Brunauer–Emmett–Teller adsorption–desorption, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy, high-resolution transmission electron microscopy, and point of zero charges. The activity in the photodegradation of cinnamic acid (CA) under UV-A irradiation of the CTO/Ti heterostructure was investigated and compared with individual materials TiO₂ (Ti-w) and CoTiO₃ (CTO). The investigation showed that the heterostructured CoTiO₃/TiO₂ catalyst with optimal composition (5% CTO) exhibited much higher photocatalytic activity for degradation of cinnamic acid than individual CoTiO₃ and TiO₂. Under the optimal conditions (Ccat = 0.75 g/L, Qair = 0.3 L/min, and pH = 3.8) the 90 min conversion of cinnamic acid reached 80.9% on 5CTO/Ti, much higher than those of CTO (4.6%) and Ti-w (75.2%). It was found that the enhancement in activity for the CA removal of the CTO/Ti heterostructure was due to the construction of a heterojunction structure between TiO₂(Ti-w) and CoTiO₃ that resulted in an increase in the specific surface area and porosity, reduction of the band gap energy, and higher efficient separation of charge carriers on the surface to prevent recombination. Alternatively, a comparison of the recyclability of 5CTO/Ti and Ti-w was made for CA degradation. The results showed a decrease in the CA conversion by 38% on 5CTO/Ti and 48% on Ti-w after six reaction cycles.