This study sheds light on how the properties of titanium dioxide (TiO2) are influenced when it is modified with iron (Fe), leading to the formation of Fe-doped-TiO2, Fe2O3-TiO2 composite, and single-phase FeTiO3 systems. The structural formation of the materials, oxidation state, and chemical environments of the elements are analyzed using XRD and XPS techniques. Band structures with UV–visible light driven properties and suitable redox potentials with improved recombination resistance along with an active inter- and intra-charge transfers were observed for Fe2O3-TiO2 and FeTiO3 systems. The photocatalytic efficiency was found to be superior for FeTiO3 system, degrading ~97 and 100 % of phenol, malachite green and rhodamine B dyes in 150 min, respectively along with enhanced recyclability. Interestingly, a competitive S- and Z-scheme was predicted for Fe2O3-TiO2 composite, explaining its photocatalytic mechanism. The scavenger and total organic carbon analyses revealed the radicals driving the photocatalytic reactions and the nature of degradation products, respectively.