Bismuth oxyhalide compounds have similar electronic configurations and crystal structures. Due to high electronegativity, they can be used for synthesizing solid solutions that have a number of advantages, which are enhanced charge separation, efficient adsorption, and high photoreduction potential. Solid solutions of the general formula BiOI1‐xFx (X=0 to 0.5) were prepared using the soft chemical method. The investigation of the optical properties of the considered solid solutions revealed a blue shift in wavelength. The solid solution BiOI0.7F0.3 exhibited an excellent adsorption coefficient and optimum photodegradation performance with RhB dye. Compared to pure BiOI, it showed higher adsorption and caused twice more efficient photodegradation. The different density functional theory (DFT) methods calculations revealed that the shift in band gap in the considered solid solutions mainly took the form of up‐shifting in the conduction band; thus, it was predicted that the reduction potential would increase with the increase in fluorine content. The results thus suggest that BiOI1‐xFx solid solutions are a viable alternative for the use in photocatalytic removal of toxic Pb2 ions from aqueous solutions.