In this work, the effect of the calcination temperature on the TiO2 synthesis using Pechini’s method was reported. The adopted calcination temperatures were 500, 600, and 700°C. XRD measurements indicated the composition of crystalline phases, and from there, the conversion of the anatase phase to rutile. TiO2 Evonik® was used as a reference standard and sodium diclofenac as a standard for photodegradation assessment. The average crystalline size increased. In both cases, this trend accompanied the increase in calcination temperature. The optical properties were performed using diffuse UV‐Vis reflectance. Results obtained indicated maximum absorption wavelength values more intense and displaced to the visible region. Also, the estimated band gap energy values decreased. The photocatalytic performance of TiO2 samples was superior to the reference catalyst (TiO2 Evonik®). Especially in the first 10 minutes, the comparative photodegradation was up to approximately 58% higher. The photodegradation kinetic constants were also higher, and by comparison, up to approximately 73% higher. Toxicity measurements, using Artemias salina, also indicated similar decay behavior in the first 10 minutes, with a performance of up to approximately 60%.