The development of carbon materials offers the hope for obtaining inexpensive and high-performance alternatives to substitute noble-metal catalysts for their sustainable application. Graphdiyne, the rising-star carbon allotrope, is a big family with many members, and first realized the coexistence of sp- and sp(2) hybridized carbon atoms in a 2D planar structure. Different from the prevailing carbon materials, its nonuniform distribution in the electronic structure and wide tunability in bandgap show many possibilities and special inspirations to construct new-concept metal-free catalysts, and provide many opportunities for achieving a catalytic activity comparable with that of noble-metal catalysts. Herein, the recent progress in synthetic methodologies, theoretical predictions, and experimental investigations of graphdiyne for metal-free catalysts is systematically summarized. Some new perspectives of the opportunities and challenges in developing high-performance graphdiyne-based metal-free catalysts are demonstrated.