This study probably for the first-time introduced a phase and morphology-tuned scalable, cost-effective method for large-scale production of Black Phosphorous/Phosphorene (BP), and investigated their in-depth electrochemical properties. Utilizing a one-pot mild wet chemical-assisted hydrothermal route in ethylenediamine, high-quality BP nanosheets were synthesized from amorphous red phosphorus (RP) with nearly 100 % conversion efficiency, yielding 7.1352 g for one batch at 130–170 °C. The resulting phosphorene nanosheets exhibited a small crystalline size (2.708 nm), hierarchically porous morphology, a 1.64 eV direct optical bandgap aligned with theoretically calculated bandgap using LDA approximation, and various structural defects, along with large specific surface area (50 m2g−1) and reduced number of layers (4–5) compared to prior literatures, suggesting electrochemical superiority. CV and GCD measurements in the potential window of −0.7 V to 0.1 V revealed its highest pseudo-capacitance response (84.91 %), reaching a maximum specific capacitance value of 759.748 Fg−1 at current density 2 Ag−1, surpassing all previous records. Moreover, BP displayed excellent cyclic stability of 89.8 % after 10,000 cycles, making it an excellent electrode material for supercapacitors. A solid-state asymmetric supercapacitor device (HASD), using BP, successfully lighted up 6 red LEDs for 10 s, achieving maximum specific energy density at 73.43 Wkg−1 at a power density of 1500 Wkg−1.