This paper presents the results of an experimental study to investigate the structural and microchemical characteristics of an equiatomic CrFeNbNiV alloy.XRD analysis of CrFeNbNiV alloy, revealed a predominant NbCrNi type HCP Laves phase conjoined with two minor tetragonal and BCC phases. Detailed microstructural investigations using electron microscopy techniques also substantiated the presence of the above mentioned phases.The structure of Laves phase in this alloy is determined ab initio for the first time using Precession Electron Diffraction technique which was in agreement with the Rietveld analysis of XRD pattern. The formation of intermetallic Laves phase was understood based on theoretical phase stability and average d- orbital energy level Md‾ value calculations. The alloy in the ‘as cast’ condition exhibited a very high value of hardness (~ 1500 Hv). No change in the microstructure and hardness was observed on annealing at high temperatures even up to 1373 K (1100 °C).