Machine-tool life is one limiting factor affecting productivity. The requirement for wear-resistant materials for cutting tools to increase their longevity is therefore critical. Titanium diboride (TiB2) coated cutting tools have been successfully employed for machining of AlSi alloys widely used in the automotive industry. This paper presents a methodological approach to improving the self-lubricating properties within the cutting zone of a tungsten carbide milling insert precoated with TiB2, thereby increasing the operational life of the tool. A unique hybrid Physical Vapor Deposition (PVD) system was used in this study, allowing diamond-like carbon (DLC) to be deposited by filtered cathodic vacuum arc (FCVA) while PVD magnetron sputtering was employed to deposit WS2. A series of ~100-nm monolayer DLC coatings were prepared at a negative bias voltage ranging between −50 and −200 V, along with multilayered DLC-WS2 coatings (total thickness ~500 nm) with varying number of layers (two to 24 in total). The wear rate of the coated milling inserts was investigated by measuring the flank wear during face milling of an Al-10Si. It was ascertained that employing monolayer DLC coating reduced the coated tool wear rate by ~85% compared to a TiB2 benchmark. Combining DLC with WS2 as a multilayered coating further improved tool life. The best tribological properties were found for a two-layer DLC-WS2 coating which decreased wear rate by ~75% compared to TiB2, with a measured coefficient of friction of 0.05.