The control of environmental pollutants is a global concern. Recently, heteroatom-doped graphene has drawn increasing attention due to their widespread applications in removing and detecting environmental pollutants. Owing to the introduction of heteroatoms into pristine graphene, the properties of heteroatom-doped graphene have been significantly enhanced in physic, chemistry, and biology. This review focuses on the approaches for synthesis and characterization of boron-, sulfur-, and phosphorus-doped graphene and their applications in the fields of adsorption, catalysis, and detection for environmental pollutants. The mechanisms of environmental applications, including π-π interactions, complexation, hydrophobic interactions, electronic conductivity, and active sites and reactive radicals, are elaborated. Furthermore, the challenges associated with the use of heteroatom-doped graphene materials and their prospective applications are also proposed.