The limited resources of fossil fuels and the increase in human’s demand for energy have made the use of alternative green energies like hydrogen very important. In this regard, achieving superior specific capacity and high-performance electrochemical hydrogen storage requires the structural design and development of highly active electrode material with cooperative influence of “spillover”, “redox”, and “physisorption” mechanisms. The aim of this report is to fabricate a binary TbCrO3/montmorillonite-K10 (TC/MMT) nanocomposite and to skillfully ensure its electrochemical ability for hydrogen storage in 2.0 M KOH electrolyte, for the first time. A facile sonochemical strategy was presented to successfully form uniform orthorhombic TC nanoparticles with varying tetradentate Schiff base ligands derived from salicylaldehyde and relative diamines as well as the molar ratio of H2Salbn to Tb3+. Characterization analyses displayed that the nucleation and growth process of TC samples can be well controlled by a molar ratio of H2Salbn:Tb3+ = 1:1 within the range of 17–72 nm. Furthermore, implementation of a well-organized MMT-based nanocomposite with various amounts of nano-TC perovskites was evaluated on the structural and electrochemical features. The greatly enhanced hydrogen storage capacity of TC/MMT nanocomposites was acquired as 734.3 mAh/g after 15 cycles, when 10.0 % of perovskite oxide is induced by MMT layers. Moreover, architecture of pristine TC and MMT electrodes possessed a 936.87 and 341.52 mAh/g discharge capacities at the same situation. These merits allow a promising potential application of the nanocomposite electrodes containing rare-earth chromite oxide and clay substrates in electrochemical energy-storage devices.