Diamond-like carbon (DLC) coatings are well known as protective coatings for biomedical applications. Furthermore, the incorporation of different elements, such as silicon (Si), in the carbon matrix changes the bio-functionality of the DLC coatings. This has also been proven by the results obtained in this work. The Si-DLC coatings were deposited on the Ti6Al7Nb alloy, which is commonly used in clinical practice, using the magnetron sputtering method. According to the X-ray photoelectron spectroscopy (XPS) analysis, the content of silicon in the examined coatings varied from ~2 at.% up to ~22 at.%. Since the surface characteristics are key factors influencing the cell response, the results of the cells’ proliferation and viability assays (live/dead and XTT (colorimetric assays using tetrazolium salt)) were correlated with the surface properties. The surface free energy (SFE) measurements, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) analysis demonstrated that the polarity and wettability of the surfaces examined increase with increasing Si concentration, and therefore the adhesion and proliferation of cells was enhanced. The results obtained revealed that the biocompatibility of Si-doped DLC coatings, regardless of the Si content, remains at a very high level (the observed viability of endothelial cells is above 70%).