Sulfur-doped DLC nanocomposite films have been successfully deposited by the electrochemical method using the mixture of methanol and thiofuran as the precursor at ambient atmospheric pressure. In contrast to DLC film, the effects of sulfur incorporation on the microstructural transformation and properties of sulfur-doped DLC nanocomposite films were investigated in detail in terms of atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectrum and photoluminescence and magnetic tests. The experimental results showed that the unexpected organic molecular structure was formed like sulfone or thiols in sulfur-doped DLC nanocomposite films, and the concentration of sulfur in films was readily manipulated by the volume ratio of thiofuran to methanol. Meanwhile, the sp3-hybridized carbon content gradually decreased in films as the volume of thiofuran increased. Furthermore, sulfurdoped DLC nanocomposite films showed the monochromatic photoluminescence performance with a wide band centered at 510 nm, which could be attributed to carrier localization within an increasing sp2 clusters and the defects along with the sulfur doping. Particularly, ferro-like magnetic performance of sulfur-doped DLC nanocomposite film might originate from the magnetic moment of localized sp2 clusters with different charged carriers near the Fermi level after sulfur incorporation.