▎ 摘　　要

The combination of exceptional functionalities offered by 3D graphene-based macrostructures (GBMs) has attracted tremendous interest. 2D graphene nanosheets have a high chemical stability, high surface area and customizable porosity, which was extensively researched for a variety of applications including CO(2)adsorption, water treatment, batteries, sensors, catalysis, etc. Recently, 3D GBMs have been successfully achieved through few approaches, including direct and non-direct self-assembly methods. In this review, the possible routes used to prepare both 2D graphene and interconnected 3D GBMs are described and analyzed regarding the involved chemistry of each 2D/3D graphene system. Improvement of the accessible surface of 3D GBMs where the interface exchanges are occurring is of great importance. A better control of the chemical mechanisms involved in the self-assembly mechanism itself at the nanometer scale is certainly the key for a future research breakthrough regarding 3D GBMs.