Conventional fabricating methods of TA2–304 SS laminated metal composite (LMC) (e.g., hot rolling, hot stamping, and explosive welding) have difficulty in removing brittle TiFe intermetallic compounds (IMCs) and are not suitable for the preparation of the small size structure components or transition joints. Additive manufacturing of LMCs has the potential to achieve the desired microstructure, properties, and structure. In this study, TA2–304 SS LMC, which has been extensively employed in pipe flanges of nuclear plants and bows of sonar dome, was well fabricated by utilizing directed energy deposition-arc (DED-arc) and copper‑nickel alloy transition interlayers, and the formation of brittle TiFe IMCs was suppressed. The results of this study indicated that the standard deviation of the height of the surface morphology reconstructed by adopting Python VTK technique was evaluated as 0.67. Furthermore, copper‑nickel transition interlayers possessed the capability of isolating Ti from Fe atoms through the formation of laminar-distributed microstructure. Specifically, the Interlayer1 was comprised of (Fe, Cr) grains with different shapes and small-size (Cu) equiaxial grains, Interlayer2 covered large-size (Cu, Ni) dendritic grains and intergranular (Cu), and the TA2 layer comprised α-Ti and Ti2Cu. The result also showed that thermal cycle-induced recovery and recrystallization and diffusion-induced elemental interaction accounted for the different microstructures. Moreover, the interface between the TA2 and Interlayer2 layers contained TiCu4 + (Cu), Ti3Cu4 + TiCu4, Ti2Cu + TiCu, and TiCu + Ti2Cu eutectoid microstructures, which resulted in the highest hardness of 450Hv as well as crack initiation and extension. Furthermore, due to the uniform-distribution of microstructure in the absence of brittle IMCs, the average shear strength was 234.0 MPa, which reached the strength of the conventional method and conformed to the standard requirements. Multiple groups of galvanic reactions between different transition materials can result in reduced corrosion resistance, and the oxidation-reduction reactions can lead to the formation of massive oxides.