Electronic structure and optical band gap of thin films grown on 001 oriented have been investigated. Surprisingly, these films show additionalRaman modes at room temperature as compared to a bulk spinel structure. The splitting of Raman modes is explained by considering the short-range ordering of Co and Fe cations in octahedral site of spinel structure. In addition, an expansion of band-gap is observed with the reduction of film thickness, which is explained by the quantum size effect and misfit dislocation. Such results provide interesting insights for the growth of spinel phases.