Porous materials play a vital role in science and technology. The ability to control their pore structures at the atomic, molecular, and nanometer scales enable interactions with atoms, ions and molecules to occur throughout the bulk of the material, for practical applications. Three-dimensional (3D) porous carbon-based materials (e.g., graphene aerogels/hydrogels, sponges and foams) made of graphene or graphene oxide-based networks have attracted considerable attention because they offer low density, high porosity, large surface area, excellent electrical conductivity and stable mechanical properties. Water pollution and associated environmental issues have become a hot topic in recent years. Rapid industrialization has led to a massive increase in the amount of wastewater that industries discharge into the environment. Water pollution is caused by oil spills, heavy metals, dyes, and organic compounds released by industry, as well as via unpredictable accidents. In addition, water pollution is also caused by radionuclides released by nuclear disasters or leakage. This review presents an overview of the state-of-the-art synthesis methodologies of 3D porous graphene materials and highlights their synthesis for environmental applications. The various synthetic methods used to prepare these 3D materials are discussed, particularly template-free self-assembly methods, and template-directed methods. Some key results are summarized, where 3D graphene materials have been used for the adsorption of dyes, heavy metals, and radioactive materials from polluted environments.