Hydrogen fuel, as an alternative renewable energy resource, has recently attracted much attention for meeting global energy crisis and environmental sustainability. However, the storage of hydrogen as a neat fuel in economical and technological feasible forms to replace the widespread use of fossil fuels in diverse applications is still a formidable challenge to scientists. As per earlier reports, metal-doped pentalenes were found to be promising candidates for hydrogen storage as per their storage capacity but were found to possess certain thermodynamic constraints. Our calculations show that transition metal-doped pentalenes can exhibit a hydrogen storage capacity of 3.68% to 7.73% with an average adsorption energy of 0.66 to 1.23 eV/H 2 without any thermodynamic limitations. We have evaluated various physico-chemical parameters and hydrogen storage calculations that include adsorption energy, Gibbs free energy, and reactivity descriptors, which assist in understanding the comparative structure and properties of these pentalene-based systems at the electronic structure level. In addition to that, these pentalenes were doped with two homo and hetero transition metals to enhance their storage capacity. Thermo-chemistry-based calculations have been performed in order to understand their working temperature and desorption behavior. The calculations based on energy gaps have proven the pentalenes to be kinetically stable. Details related to bond distance, charge density, single point energy, orientation, and mode of adsorption were also calculated for both the parent and their boron substituent complexes to provide a detailed idea about their hydrogen storage behavior. This study could open a new window, toward the use of pentalenes as hydrogen storing systems in near future.