Heterojunctions of metal oxides have attracted a great deal of attention as photo (electro) catalysts owing to their excellent photoactivity. While multiple fundamental studies have been dedicated to heteroaggregation, self-assembly of oppositely charged particles to obtain heterojunctions for energy applications has been underexplored. Herein, we report the synthesis of ZnO-TiO 2 heterojunctions using the electrostatic self-assembly approach. The synthesized ZnO-TiO 2 heterojunctions were characterized by using multiple experimental techniques. Density functional theory calculations were conducted to establish the heterojunction formation mechanism and electronic properties. The ZnO-TiO 2 nanohybrid was tested for the photodegradation of rhodamine B dye and water splitting applications. The photocatalytic performance of the ZnO-TiO 2 nanohybrid is 3.5 times higher than that of bare ZnO. In addition, the heterostructure exhibited an excellent photocurrent density of 2.4 mA cm −2 at a low onset potential during photoelectrochemical oxygen evolution. The performance improvements are attributed to the formation of the type II heterojunction between ZnO and TiO 2 , which suppresses carrier recombination and enhances carrier transport, boosting the catalytic activity.