Three types of walls were produced by the direct laser metal deposition (DLMD) process; SS316L, Inconel 625 (IN625), and SS316L-Inconel 625 FGM. The thin walls were deposited on an AISI 4130 austenitic steel substrate in five layers with a length of 2 cm. The solidification behavior, secondary dendrite arm spacing (SADS) value, chemical composition, and hardness of samples were studied. Microstructures were evaluated using optical microscopy (OM) images, scanning electron microscopy (SEM), EDS Line, EDAX, and Map analyses. OM and SEM images showed an acceptable bonding between the layers in all samples. The main solidification was equiaxed dendritic and columnar dendritic in most parts. The growth of dendrites was perpendicular to the substrate. Some dendrites grew epitaxially at the interface of two sequential layers. The standard deviation of SDAS value for SS316L, IN625, and SS316L-IN625 FGM was 0.63, 0.71, and 0.73, respectively. The lowest value of SDAS was obtained in layer one, while the highest value was obtained in layer five of the thin walls. The average SDAS values for SS316L, IN625, and SS316L-IN625 FGM were 4.40, 4.53, and 4.76 µm, respectively. Therefore, the difference between the SDAS values was not significant. EDAX and Map analyses showed that the segregation of Nb and Mo to the dendritic boundary and the formation of eutectic, secondary phases, and brittle Laves phases have occurred. Additionally, the segregation of Nb and Mo to the dendritic boundary in the SS316L-IN625 FGM sample was higher than SS316L and IN625 samples. The microhardness values oscillated significantly and decreased by moving away from the substrate (in the build direction). The microhardness values of different points of the SS316L-IN625 FGM walls were in the range of 218–278 HV. EDS line scan, microstructure, and microhardness analyses indicated the successful fabrication of the SS316L-IN625 FGM by the DLMD process.