TiO₂ exists naturally in three crystalline forms: Anatase, rutile, brookite, and TiO₂ (B). These polymorphs exhibit different properties and consequently different photocatalytic performances. This paper aims to clarify the differences between titanium dioxide polymorphs, and the differences in homophase, biphase, and triphase properties in various photocatalytic applications. However, homophase TiO₂ has various disadvantages such as high recombination rates and low adsorption capacity. Meanwhile, TiO₂ heterophase can effectively stimulate electron transfer from one phase to another causing superior photocatalytic performance. Various studies have reported the biphase of polymorph TiO₂ such as anatase/rutile, anatase/brookite, rutile/brookite, and anatase/TiO₂ (B). In addition, this paper also presents the triphase of the TiO₂ polymorph. This review is mainly focused on information regarding the heterophase of the TiO₂ polymorph, fabrication of heterophase synthesis, and its application as a photocatalyst.