The highly adjustable properties of high-entropy alloys (HEAs) offer great potential for developing superior materials for critical structural applications in high-temperature conditions. In this study, Ni-Fe-Cr-Al-V HEA was manufactured by laser powder bed fusion, which has a unique microstructure composed of dislocation substructure and Face-centered cubic + L12 coherent structure and achieves the desired strength-ductility combination. Hot isostatic pressing post-treatment was applied on the laser powder bed fusion-processed HEA to further improve the relative density and optimize the mechanical properties. During the hot isostatic pressing process, the precipitation of L12 and B2 phases can be ascribed to the precipitation modes dominated by continuous precipitation and discontinuous precipitation, respectively. With the tensile deformation temperature increasing from 773-1,173 K, the softening degree of HEA increases continuously, and the dominant deformation mechanism evolves from intragranular dislocation slip to grain boundary sliding. At temperatures below 773 K, precipitation strengthening significantly improves tensile strength and ductility. At 1,173 K, the grain boundary strength decreases and grain boundary area increases, which promotes grain boundary sliding and contributes to plastic deformation, resulting in significant softening.