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Doping is a great strategy for tuning the characteristics of graphene-based nanomaterials. Phosphorous has a higher electronegativity as compared to carbon, whereas boron can induce p-type conductivity in graphene. This review provides insight into the different synthesis routes of phosphorous- and boron-doped graphene along with their applications in supercapacitors, lithium- ions batteries, and cells such as solar and fuel cells. The two major approaches for the synthesis, viz. direct and post-treatment methods, are discussed in detail. The former synthetic strategies include ball milling and chemical vapor discharge approaches, whereas self-assembly, thermal annealing, arc-discharge, wet chemical, and electrochemical erosion are representative post-treatment methods. The latter techniques keep the original graphene structure via more surface doping than substitutional doping. As a result, it is possible to preserve the features of the graphene while offering a straightforward handling technique that is more stable and controllable than direct techniques. This review also explains the latest progress in the prospective uses of graphene doped with phosphorous and boron for electronic devices, i.e., fuel and solar cells, supercapacitors, and batteries. Their novel energy-related applications will continue to be a promising area of study.