The systematized design of two-dimensional (2D) nanocatalysts for sensible energy-efficient reactions is quite a puzzling prospective aspect in energy-related applications. In this current work, we used a top-down strategy to synthesize silicon (Si) nanoparticles using a high-energy mechanical ball milling technique. In hydrothermal reaction, these Si nanoparticles were introduced into the 2D MoSe2 matrix sequence based on varying the percentages of silicon (0–15%) vs Selinium content. The high crystalline phases of the synthesized 10% Si:MoSe2 exhibited the sheet-like morphology and silicon inserted layered structure. The pristine MoSe2@CC & Si:MoSe2@CC electrodes were prepared by tape casting method. During HER reaction, the miniscule insertion of Si into MoSe2 matrix amplified the current density until 10% addition and moved the reduction curves towards lower onset overpotential (76.23 mV) in addition to the significant Tafel value (112.3 mV/decade). The potential of the better performed electrode in HER was explored as an anode for Lithium-ion battery (LIB) applications. The electrode delivered a discharge capacity of 406.7 mAh g−1 at a current density of 100 mA/g after 100 charge-discharge cycles. Furthermore, the rationally constructed bifunctional electrode (Si:MoSe2@CC) showed strong physicochemical stability, which can be used in future sustainable energy generation and storage devices.