A new heterostructured titanium–iron-based material dispersed in alkaline muscovite (Ti–Fe–Mus) was synthesized by a typical impregnation process, and characterized by X-ray diffraction, adsorption/desorption of liquefied nitrogen and thermogravimetric/differential thermal analysis. This characterization suggests that the Ti–Fe–Mus system does not present sufficiently ordered silicate layers, but has a delaminated structure. The specific surface area and porosity have been significantly improved compared to the virgin muscovite, and the outer surface appears to be the dominant active surface. In particular, the Ti–Fe–Mus system was examined as a photocatalyst for the degradation of Tetrabromobisphenol A (TBBPA) selected as a model compound by visible light exposure. The Ti–Fe–Mus system showed excellent photocatalytic activity for TBBPA degradation and optimum catalyst concentration was found at 0.4[Formula: see text]g L[Formula: see text]. More than 60% by weight of parent TBBPA with an initial concentration of 300[Formula: see text]ppm were eliminated after 120[Formula: see text]min at [Formula: see text]. Acid conditions have resulted in a faster elimination compared to alkaline and neutral conditions. Based on these results, it has been shown that titanium and iron modified delaminated muscovite (Ti–Fe–Mus) have strong potential for application as a powerful photocatalyst for the elimination of persistent organic pollutants present in the environment.