The selection and design of new electrode materials for energy conversion and storage are critical for improved performance, cost reduction, and mass manufacturing. A bifunctional anode with high catalytic activity and extended cycle stability is crucial for rechargeable lithium‐ion batteries and direct borohydride fuel cells. Herein, a high entropy novel three‐dimensional structured electrode with Pr‐doped hollow NiFeP nanoflowers inlaid on N‐rGO was prepared via a simple hydrothermal and self‐assembly process. For optimization of Pr content, three (0.1, 0.5, and 0.8) different doping ratios were investigated. A lithium‐ion battery assembled with NiPr0.5FeP/N‐rGO electrode achieved an outstanding specific capacity of 1.61 Ah g−1 at 0.2 A g−1 after 100 cycles with 99.3 % Coulombic efficiencies. A prolonged cycling stability of 1.02 Ah g−1 was maintained even after 1000 cycles at 0.5 A g−1. In addition, a full cell battery with NiPr0.5FeP/N‐rGO∥LCO (Lithium cobalt oxide) delivered a promising cycling performance of 0.52 Ah g−1 after 200 cycles at 0.15 A g−1. Subsequently, the NiPr0.5FeP/N‐rGO electrode in a direct borohydride fuel cell showed the highest peak power density of 93.70 mW cm−2 at 60 °C. Therefore, this work can be extended to develop advanced electrode for next‐generation energy storage and conversion systems.