In this research, two intermediate layers were deposited on 316L stainless steel to improve the adhesion of diamond-like carbon (DLC) films, one composed of TixAl and produced using the RF sputtering technique with three thicknesses, 100 nm, 200 nm, and 300 nm; the other, interlayer composed of amorphous hydrogenated silicon (a-Si:H). The DLC films were deposited using the pulsed-DC PECVD method with an active screen to achieve the AISI 316L/TixAl //DLC and AISI 316L/TiₓAl/a-Si/DLC configurations. The binding energy between the substrate/TixAl and TixAl/a-Si:H was investigated via X-ray photoelectron spectroscopy with high-resolution spectra. The chemical composition and microstructure of the titanium–aluminum interlayers were investigated using energy-dispersive X-ray spectroscopy and X-ray diffraction, and the microstructure of the DLC coatings was studied using Raman spectroscopy. The coatings’ adherence was measured using scratch and indentation tests, and the hardness of the DLC coatings was determined with the nanoindentation test. The X-ray diffractograms did not allow the determination of any crystalline structure in the TixAl interlayers. The XPS results showed that between the AISI 316L substrate and the TixAl intermediate layer, Ti-O-Fe and FeAl2O4 were formed. On the other hand, at the TixAl/a-Si:H interface, TiSi2 and Al2SiO5 compounds were identified. The DLC coatings grew as hydrogenated amorphous carbon with a hydrogen content of around 30 at.% and a hardness of 24 GPa. The deposition methods used and the TixAl/a-Si:H interlayers allowed the obtainment of adherent DLC coatings on AISI 316L stainless steel substrates. High critical load values of about 30 N were obtained. The novelty of this work is underscored by the absence of previous studies that thoroughly examine the bonds present in interlayers used as gradients to enhance the adhesion of DLC.