Direct Energy Deposition (DED) 3D printing has gained significant importance in various industries due to its ability to fabricate complex and functional parts with reduced material waste, and to repair existing components. Titanium alloys, known for their exceptional mechanical properties and biocompatibility, are widely used in DED 3D printing applications, where they offer benefits such as lightweight design possibilities and high strength-to-weight ratio. However, given the high material cost of titanium alloys, certain applications can benefit from the coating capabilities of DED to achieve the advantages of titanium on a distinct material substrate. Nevertheless, challenges related to material incompatibility and the development of unwanted brittle phases still affect the successful deposition of titanium alloys on steel substrates with DED 3D printing. This paper investigates the processing challenges and reviews delamination prevention methods, specifically targeting titanium-steel interfaces. In particular, the formation of unwanted brittle Ti–Fe intermetallics and methods to circumvent their formation are explored. The findings of this research contribute to a deeper understanding of the processing challenges and delamination prevention methods in DED 3D printing.