The additive manufacturing (AM) technique, laser metal deposition (LMD), combines the advantages of near net shape manufacturing, tailored thermal process conditions and in situ alloy modification. This makes LMD a promising approach for the processing of advanced materials, such as intermetallics. Additionally, LMD allows the composition of a powder blend to be modified in situ. Hence, alloying and material build-up can be achieved simultaneously. Within this contribution, AM processing of the promising high-temperature material β-NiAl, by means of LMD, with elemental powder blends, as well as with pre-alloyed powders, was presented. The investigations showed that by applying a preheating temperature of 1100 °C, β-NiAl could be processed without cracking. Additionally, by using pre-alloyed, as well as elemental powders, a single phase β-NiAl microstructure can be achieved in multi-layer build-ups. Major differences between the approaches were found within substrate near regions. For in situ alloying of Ni and Al, these regions are characterized by an inhomogeneous elemental distribution in a layerwise manner. However, due to the remelting of preceding layers during deposition, a homogenization can be observed, leading to a single-phase structure. This shows the potential of high temperature preheating and in situ alloying to push the development of new high temperature materials for AM.