Mixed oxides, α-Fe2O3/Bi2WO6, were prepared using a mechanical mixing procedure by adding to the Bi2WO6 previously obtained by hydrothermal method the corresponding amount of a prepared α-Fe2O3, the latter obtained by thermal decomposition of Fe(NO3)∙9H2O. The physicochemical surface, structural, morphological characteristics and optical properties of the samples, single and mixed, were determined by BET, XRD, FE-SEM, XPS and UV–vis diffuse reflectance spectroscopy. UV–vis diffuse reflectance spectra showed that incorporating a 5%wt. of α-Fe2O3 to the corresponding amount of Bi2WO6 sample broadened the visible light absorption of Bi2WO6 as expected. The photocatalytic activity, of single and mixed catalysts, to degrade a selected dye such as Methyl Orange (MO) as well as the transparent substrate Phenol (Ph) was studied, in aqueous medium (pH ≈ 5.5) under UV and sun-like illumination conditions in the absence and presence of H2O2. In the present study the use of a α-Fe2O3-Bi2WO6/H2O2 system demonstrate much higher photocatalytic efficiency to degrade both MO and Ph than pristine Bi2WO6or α-Fe2O3, single or mixed. Using the system α-Fe2O3-Bi2WO6/H2O2, around 85% of MO was degraded in 60 min under sun-like illumination whereas 100% was degraded in 60 min under UV-illumination. However, just around 30% of Ph was degraded in 120 min in the α-Fe2O3-Bi2WO6/H2O2 system under sun-like illumination whereas around a 95% was degraded in 90 min under UV-illumination. Under UV-illumination, the generation of hydroxyl radicals is favorable; whereas under sun-like illumination, only the small fraction of the UV can produces the radical dotOH. Under illumination, the H2O2 could react with photoinduced electrons from the photocatalysts leading to the production of hydroxyl radicals (radical dotOH).Peer reviewe