Additive manufacturing (AM) is a highly innovative method for joining dissimilar materials for industrial applications. In the present work, AM of STS630 and Ti-6Al-4V powder alloys on medium entropy alloys (MEAs) NiCrCo and NiCrCoMn is studied. The STS630 and Ti64 powders are deposited on the MEAs. Joint delamination and cracks are observed after the deposition of Ti64 on the MEAs, whereas the deposition of STS630 on the MEAs is successful, without any cracks and joint delamination. The microstructure around the fusion zone interface is characterized by scanning electron microscopy and X-ray diffraction. Intermetallic compounds are formed at the interfacial regions of MEA-Ti64 samples. In addition, Vicker’s hardness value increased dramatically at the joint interface between MEAs and Ti-6Al-4V compared to that between MEAs and STS630. This result is attributed to the brittle nature of the joint, which can lead to a decrease in the joint strength.