In this study, we have prepared a Ti-6Al-4V/V/17-4 PH composite structure via a direct energy deposition process, and analyzed the interfaces using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The joint interfaces comprise two zones, one being a mixed zone in which V and 17-4PH are partially mixed and another being a fusion zone in the 17-4PH region which consists of Fe+FeV. It is observed that the power of the laser used in the deposition process affects the thickness of the mixed zone. When a 210 W laser is used, the thickness of the mixed zone is wider than that obtained using a 150 W laser, and the interface resembles a serrated shape. Moreover, irrespective of the laser power used, the expected  phase is found to be absent in the V/17-4 PH stainless steel joint; however, many VN precipitates are observed.