In this study, we explore the electrochemical synthesis of size-tuned PQDs coupled with PW (PQDs@PW) to address the specific requirements of Na-ion batteries as an anode material. By employing an electrochemical exfoliation process, we are able to achieve PQDs with controlled dimensions from black phosphorous at room temperature using 0.1 M LiClO4 in N-Methyl-2-Pyrrolidone (NMP) by varying the concentrations, optimizing them for enhanced Na-ion diffusion and charge storage. Our results demonstrate that PQDs@PW can offer significant advantages in terms of both energy and power densities, providing insights into their potential for next-generation energy storage technologies. This study thus establishes a scalable and efficient route for producing phosphorene-based materials, laying the foundation for further advancements in SIB technology. The UV and PL results demonstrate the size-dependent optical properties of these quantum dots (QDs). Additionally, transmission electron microscopy (TEM) reveals the size distribution and morphological structure of phosphorene quantum dots (PQDs), supporting their potential for band-gap engineering. This study is the first to report on the application of sizedependent PQDs@PW in energy storage.