The structural modification of nanomaterials at the atomic level has the potential to generate tailor‐made components with enhanced performance for a variety of tasks. The chemical versatility of graphene has been constantly employed to fabricate multi‐functional doped 2D materials with applications encompassing energy storage and electrocatalysis. Despite the many reports on boron‐ and nitrogen‐doped graphenes, the possible synergy that arises from combining these electronically complementary elements has yet to be fully understood and explored. The techniques used for the fabrication of these nanomaterials are reviewed, along with the most recent reports on the benefits of B, N singly doping and co‐doping in the electrocatalysis for oxygen reduction reactions and for energy storage in supercapacitors and lithium secondary batteries. The investigation of bulk co‐doped materials has intrinsic limitations in fully understanding the real role of heteroatoms in the above applications. Ultimately, the design and creation of substituted monolayers with controlled compositions might hold the key for carbon‐based energy‐related applications. The electrochemical performance of graphene in terms of catalysis and energy storage can be enhanced by heteroatom B, N doping. Different doping routes result in different doping concentrations and B, N chemical environments, and thus a wide distribution of electrochemical performance. Subtle substitution in monolayers is an effective way to unravel the role of heteroatoms.