In this work, TiO2/Al2TiO5 (Ti/ATO) heterostructure catalysts with the different content of TiO2 were successfully synthesised by sol-gel-based hydrothermal method. Characteristics of the synthesised catalysts were determined by various methods including X-ray diffraction (XRD), Raman spectroscopy (Raman), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller adsorption (BET), UV-Vis diffuse reflectance spectroscopy (DRS), and scanning electron microscopy (SEM). The results showed that the addition of TiO2 to Al2TiO5 significantly reduced the particle size, shifted the absorption band above 404 nm, and increased the specific surface area of the hybrid catalysts. The value of the anatase/rutile ratio can be controlled by TiO2 content changing on hybrid samples. The sample containing 33% TiO2 (33Ti/ATO) had the highest activity for cinnamic acid (CA) remove under irradiation of UV-visible light due to the proportion of TiO2 anatase and rutile phases, more hydroxyl groups on the catalyst surface, small nanoparticle size, and high the specific surface area. The optimum reaction conditions including the catalyst dosage, the airflow, and the initial pH solution in the photocatalytic degradation of cinnamic acid at 25°C were determined on 33Ti/ATO catalyst. In the most favourable conditions, the CA removal efficiency reached 88.5% after 60 min, much higher than that on the Al2TiO5 sample with the removal efficiency of 38.0%.