Selenocyanate (SeCN‾) species, commonly found in industrial effluents from crude oil refineries and mining operations, present substantial health risks to humans and animals. This study investigates the treatment of selenocyanate-contaminated streams using a combination of TiO2 photocatalysis and Fe(III)/SiO2 binary oxide adsorption {UV-TiO2/[Fe(III)/SiO2]}. The Fe(III)/SiO2 binary oxide was synthesized and characterized using X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy. XRD analysis revealed non-crystalline Fe-oxide phases, while FTIR indicated the presence of various Fe and O functional groups on the Fe(III)/SiO2 surface. Adsorption studies using Fe(III)/SiO2 showed its selenocyanate uptake capacity ∼ 2.1 mg/g, with the respective data closely aligning with the Langmuir isotherm model. This Fe(III)/SiO2 adsorption feature was successfully combined in the {UV-TiO2/[Fe(III)/SiO2]} system in which the hydroxyl radicals (●OH) generated by the UV-TiO2 facilitated the breakdown of the selenocyanate complex, while the resulting selenite and selenate were simultaneously adsorbed by the Fe(III)/SiO2 within a 240-min reaction time. A mathematical model developed using a face-centered central composite design-response surface methodology (FCD-RSM) showed significant predictive capability with an insignificant lack of fit. Optimal conditions for selenium removal were determined to be 20 mg/L selenocyanate, 1 g/L TiO2, and 1 g/L Fe(III)/SiO2, at pH 5, within a 240-min reaction time. Kinetic analysis demonstrated that selenocyanate degradation followed pseudo-first-order kinetics, while total selenium removal adhered to pseudo-second-order kinetics, confirming the proposed selenium species removal mechanism. Overall, this integrated approach offers a promising solution for effective selenocyanate remediation in industrial wastewater.