Ti6Al4V is the most used alloy for implants because of its excellent biocompatibility; however, its low wear resistance limits its use in the biomedical industry. The additive manufacturing (AM) of Ti6Al4V is a well-established technique that is being used in many fields. However, the AM of Ti6Al4V composites is currently under investigation, and its manufacture using laser powder bed fusion (L-PBF) would result in a great benefit for many industries. The one-step novel concept proposed uses a gas-controlled L-PBF system that enables the AM of layers with different compositions. Six millimeter-edged cubes of Ti6Al4V were manufactured in an Ar atmosphere and coated with in situ Ti6Al4V/TiN layers by using an Ar–N2 mixture given the direct reaction between titanium and nitrogen. Unreinforced Ti6Al4V presented a martensitic microstructure, and TiN reinforcement dendrites and a minor Ti2N phase were gradually introduced into an α + β basketweave titanium matrix. The composites’ microhardness, nanohardness, and elastic modulus were 2, 3, and 1.5 times higher, respectively, than those of the Ti6Al4V. Porosity levels (caused by a lack of fusion, trapping gases, and interdendritic porosity), ranged from 7 to 12% (most measured 20–40 µm) and increased with the reinforcement content (15 to 25%). A scaled-up, proof-of-concept design of a hip implant stem was 3D printed using this nitriding method. Since the neck of the stem (top part) is more susceptible to the fracture and fretting corrosion process, the resulting graded material part consisted of unreinforced Ti6Al4V at the bottom and Ti6Al4V/TiN at the top. This change was controlled by gradually adding nitrogen to the atmosphere; moreover, it was found that the more nitrogen in the chamber, the more TiN reinforcement formed in the part. A microhardness of ~450 HV0.1 was measured at the bottom and gradually increased to ~900 HV0.1, with the increment corresponding to the in situ TiN reinforcement amount.