Controlled Synthesis of Tri‐ and Multi‐Doped Graphene

ABSTRACT Graphene possesses exceptional electrical, mechanical, and thermal properties, yet its lack of a bandgap and chemically inert surface continue to limit practical applications. Heteroatom doping has emerged as the primary strategy to overcome these limitations by tuning graphene's electronic structure and creating catalytically active sites. While single‐ and dual‐doped graphene systems are now well established, tri‐ and multi‐doped graphene remain comparatively underexplored, despite their potential to generate cooperative electronic interactions and highly tunable active‐site configurations. This review critically examines recent advances in the controlled synthesis of tri‐ and multi‐doped graphene systems. We compare bottom‐up approaches, including pyrolysis, hydrothermal synthesis, and flash Joule heating, with top‐down post‐synthetic modification methods, focusing on how synthesis conditions govern dopant incorporation, bonding configuration, defect formation, and structural ordering. Particular emphasis is placed on the relationship between dopant configuration and resulting catalytic, electrocatalytic, energy‐storage, and sensing performance. The review highlights that dopant proximity and local bonding environment are often more important than dopant number alone. Finally, current limitations in scalability, atomic‐level control, and reproducibility are discussed together with emerging strategies for rational multi‐dopant engineering.