Graphene is a 2D sheet of sp2 bonded carbon atoms and tends to aggregate together, due to the strong π–π stacking and van der Waals attraction between different layers. Its unique properties such as a high specific surface area and a fast mass transport rate are severely blocked. To address these issues, various kinds of 2D holey graphene and 3D porous graphene are either self‐assembled from graphene layers or fabricated using graphene related materials such as graphene oxide and reduced graphene oxide. Porous graphene not only possesses unique pore structures, but also introduces abundant exposed edges and accelerates mass transfer. The properties and applications of these porous graphenes and their composites/hybrids have been extensively studied in recent years. Herein, recent progress and achievements in synthesis and functionalization of various 2D holey graphene and 3D porous graphene are reviewed. Of special interest, electrochemical applications of porous graphene and its hybrids in the fields of electrochemical sensing, electrocatalysis, and electrochemical energy storage, are highlighted. As the closing remarks, the challenges and opportunities for the future research of porous graphene and its composites are discussed and outlined.

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