A new azine-linked covalent organic framework, ACOF-1, was synthesized by condensation of hydrazine hydrate and 1,3,5-triformylbenzene under solvothermal conditions. ACOF-1 has a high surface area and a small pore size, and it can store up to 177 mg g(-1) of CO2, 9.9 mg g(-1) of H2, and 11.5 mg g(-1) of CH4, at 273 K and 1 bar, with high selectivity towards CO2 over N2 and CH4.