Two-dimensional (2D) nanomaterials like silicene, MXenes, transition metal dichalcogenides (TMDs), and phosphorene have earned substantial interest where charge carrier mobility concerning whole body participation plays a significant role in required physical, electrical, chemical, and optical properties. The obligatory recommendations are bequeathed mainly to 2D materials with an atomic-thin layer structure and large surface area. To eliminate difficulties for device applications, the fabrication of heterostructure with weak interlayer van der Waals interaction is conceived for molding composites. Thus, new composites engender tunable band gap engineering with reduced charge carrier scattering encompassing defects. In this regard, phosphorene with a puckered structure and prominent anisotropy may unleash a new potential application in the new and stable 2D arena for next-generation photovoltaic (PV) cells, better anode material for energy storage, improved performance than lithium and sodium ion batteries, and supercapacitors. This article examines the existing literature, density functional theory (DFT) approximation mainly for complex heterostructures, and recent advances in 2D materials with a specific focus on phosphorene in relation to surface protection, layer structure alignment, and strain conditions for field applications. This review also explains and discusses major applications of phosphorene in sensors, catalysis, field effect transistors, and batteries.