Lithium hydride has high hydrogen capacity (12.7 mass %), but could not be considered as practical hydrogen storage media because of being very stable (required 900 °C for 0.1 MPa desorption pressure). Recently, C and Si have been found suitable to reduce the stability of LiH. This motivates us to investigate the properties of other alloys of Li, formed with the other elements. In the present work, Li3.75Ge (Li15Ge4) alloy was synthesized by mechanical milling, which transformed into Li4.2Ge (Li21.1875Ge5) and Li3.5Ge (Li7Ge2) phases during the vacuum heating at 400 °C. Hydrogenation of thus formed alloys at 400 °C under 3 MPa hydrogen pressure during PCI experiment transforms this mixed phase into Li2GeH0.5 (Li4Ge2H) and LiH phase. A remarkable decrease in the desorption temperature (300–450 °C) is observed by preparing the above alloy with Ge as observed from TG-DTA-MS experiment. The enthalpy of the reaction has also been calculated using the van’t Hoff plot. The present work concluded with the establishment of a direct relationship between hydrogen storage parameters and electrochemical parameters using the Nernst equation and van’t Hoff equation. A good agreement is found between the values of required potential for lithiation/delithiation as obtained by two methods.