We have developed an efficient route for the synthesis of TiO2/Zn2TiO2/ZnO/C nanocomposites through a Pechini sol–gel method followed by heat treatment at 550 °C for 30 min. The produced phases and their crystallite sizes have been controlled by varying the Ti4+[thin space (1/6-em)]:[thin space (1/6-em)]Zn2+ molar ratios. FE-SEM, FT-IR, XRD, TEM, diffuse reflectance spectroscopy (DRS) and thermal analysis techniques were utilized for characterization of the as-prepared products. The photocatalytic activity of the products was investigated. Superior activity was observed for the TiO2/Zn2TiO2/ZnO/C nanocomposite for the photocatalytic degradation of Orange G dye (OG) under sunlight and UV illumination with ca. 100% degradation in 50 and 120 min, respectively. The kinetic studies showed that the observed first-order rate constant (kobs) was 113.48 × 10−3 and 29.46 × 10−3 min−1 for the photocatalytic degradation under sunlight and UV irradiation, respectively. The results also showed the stability and reusability of the as-prepared nanocomposite and its applicability for the removal of OG textile dye from aqueous media.