Additive manufacturing (AM) processes are being widely investigated and gradually applied for engineering applications. Presently, the main focus is on single material systems deposition, where there are still many issues with process stability and repeatability. However, a further huge leap in the field of AM process development will be the design of multiple material–heterogeneous components. The current study presents investigation of an experimental build consisting of multiple layers of austenitic stainless steel 316L and Inconel 718, which was created by a powder blow direct energy deposition system allowing simultaneous multiple materials' deposition. Results report details of the microstructure investigation using optical metallography and scanning electron microscopy (SEM) analysis focusing on transition regions between the materials, where a significant difference was found in transition steel to Inconel and Inconel to steel. Hardness profile across deposited layers is established. Mechanical property assessment of the materials within the single material layers over the materials' transition in the horizontal direction as well as across multimaterial layers in the building direction was carried out with the use of minitensile specimens. Results obtained in this study demonstrate the importance of the order of deposited materials and the effect on their mechanical properties.