This work describes the synthesis of Fe-doped mesoporous anatase and brookite polymorphs of TiO₂ in the occurrence of P-123 surfactant at varying Fe³⁺ ions contents (0.5–2%). The photocatalytic performance of the newly synthesized Fe–TiO₂ was evaluated for phenol degradation compared to the parent TiO₂, commercial P25 and 2%Fe–P25 under the solar simulator. XRD and TEM results illustrated that the construction of TiO₂ NPs with brookite and anatase phases and the diameter of 10 nm was achieved. The surface area of 2%Fe–TiO₂ NPs (100 m²/g) revealed a large two times compared to that of P25 (50 m²/g). Interestingly, the optimum 2%Fe–TiO₂ photocatalyst exhibited complete degradation phenol within 40 min, and it was two times greater than that bare TiO₂ and commercial P25 under simulated solar light. The rate constant for degradation of phenol over 2% Fe–TiO₂ was enhanced 5.5 and 2.93 folds than that P25 and bare TiO₂ NPs. The photocatalytic enhancement performance of Fe–TiO₂ photocatalyst was supposedly created from the got better utilization of the visible light range. This is because Fe³⁺ ions can serve as a transient capturing site for photoinduced hole-electron, which suppressed the charge carriers' recombination and extended their lifetime. Photoelectrochemical measurements such as electrochemical impedance spectroscopy, chronoamperometry and cyclic voltammetry were conducted to verify and confirm the photocatalytic performance of the newly synthesized photocatalysts