Layered transition metal selenides have garnered widespread attention as the potential non-noble metal-based materials to cater to diverse energy conversion and storage aspects. Therefore, we have implemented an integrated experimental and theoretical methodology to explore the application of molybdenum diselenide (MoSe2) for HER, OER, and supercapacitor avenues via employing nanostructural and surface engineering performance enhancement strategy. Herein, we have demonstrated the successful execution of a laboratory-scale electrolyzer for water splitting with a low cell voltage of 1.54 V at 10 mA cm−2 and 1.74 V at 50 mA cm−2 current rate for 50 h. This was accomplished using synthesized exfoliated conductive carbon enwrapped MoSe2-E/C material. Further, the DFT calculations revealed the origin of better electrochemical performance on MoSe2-E (103) plane. Moreover, MoSe2-E/C showcased a high capacitance of 734 F g−1 (@ 1 A g−1) and 472 F g−1 (@ 20 A g−1) in a three-electrode setup and symmetric cell configuration respectively along with capacity retention of 95.02 % at a current density of 10 A g−1 after 2000 cycles. Hence, the prepared material exhibited its pertinence for rendering distinctive energy-related challenges owing to its unique structural arrangement.