A novel high entropy alloy (HEA) i.e. AlCrFeMnNiW is synthesized via high-energy planetary ball milling with an average crystallite size of 10.37 nm. The morphology study of hydrogenated and dehydrogenated HEA is carried out through Scanning Electron Microscope (SEM). The HEA is charged with hydrogen using inhouse Sievert's Apparatus which results to be maximum hydrogen storage capacity of 0.615 wt% at atmospheric pressure and temperature. The dehydrogenation of the sample is performed through thermogravimetry (TG) at different scanning rate. The crystalline structure (i.e. lattice parameters) and chemical composition of HEA is studied using X-Ray Diffraction (XRD) and Energy Dispersive X-Ray analysis (EDX) respectively. The unit cell volume of as-prepared alloy is estimated as 0.03131 nm3 whereas the average crystallite size as 10.37 nm. It is observed that the unit cell volume is increased by 0.67% and crystallite size decreased by 10.8% upon hydrogenation whereas it is then decreased by 0.2% and increased by 6.7% respectively upon dehydrogenation. Activation energy during hydrogen desorption is found to be −8.161 kJ/mol. The enthalpy and entropy of the mixing are estimated to be −2.645 kJ/mol and 1.793 R J/mol K. © 2019 Hydrogen Energy Publications LLC