The possible interaction of the unprecedented but recently predicted inorganic double-helices made up of lithium and phosphorous (Li n P n ; n = 7-9) with dihydrogen (H 2 ) molecules is explored via density functional theory-based computations. Because of the large amount of Li → P electron transfer, the Li chain carries a high positive charge, which can be utilized to interact with quite less-reactive elements such as H 2 . Despite low polarizability of the target species to be bound, these double-helices are found to interact with H 2 molecules, having binding energies within a range of 1.7-3.2 kcal/mol per H 2 molecule. Further, the periodic calculation with the LiP helix reveals that each Li center binds with two H 2 molecules with an average binding energy of 2.5 kcal/mol per H 2 , and this leads to a 9.6 wt % of H 2 uptake. The interactions in Li···H 2 are mainly originating from both orbital and electrostatic contributions as reflected in the energy decomposition analysis. However, a global minimum search for H 2 @Li 7 P 7 by a modified kick algorithm reveals that the lowest energy isomer is a significantly distorted structure from a helix, and having two P-H bonds. Therefore, chemisorption should be preferable over the interaction in molecular form. However, for that purpose, the rupture of the H-H bond in the H 2 molecule is essential, which needs at least an activation energy barrier of 14.9 kcal/mol to overcome. Given the fact that the H 2 storage in Li-decorated clusters would only be achieved at low temperature, the chemisorption is not likely to take place. Further, their interaction with noble gases (Ar-Rn) is also studied herein. Moreover, an inspection of their band gap structures indicates that the LiP helix could exhibit wide band gap semiconducting properties with a direct band gap value of 2.64 eV.