Carbide- and nitride-based coatings offer excellent mechanical and tribological properties due to the combination of covalent and metallic chemical bonds. Ti–W–N and Ti–W–C single layers, and (Ti–W–N/Ti–W–C)n, with n = 1 and 40, multilayers were deposited by RF-. Magnetron sputtering on AISI 1060 and silicon substrates. The coatings were characterized using FTIR and Raman spectroscopies. The hardness and friction coefficient on the n = 40 multilayered system exhibited enhanced wear results compared to those of the single layers and bilayers. In all the heterostructures, the wear mechanism analysis presented coating debris, adhesive, and abrasive groove type on the track. All pinballs presented powder particles due to abrasive debris caused by the test between the mechanical pair.