Carbon structures with covalent bonds connecting C₆₀ molecules have been reported^1,2,3, but their production methods typically result in very small amounts of sample, which restrict the detailed characterization and exploration necessary for potential applications. We report the gram-scale preparation of a new type of carbon, long-range ordered porous carbon (LOPC), from C₆₀ powder catalysed by α-Li₃N at ambient pressure. LOPC consists of connected broken C₆₀ cages that maintain long-range periodicity, and has been characterized by X-ray diffraction, Raman spectroscopy, magic-angle spinning solid-state nuclear magnetic resonance spectroscopy, aberration-corrected transmission electron microscopy and neutron scattering. Numerical simulations based on a neural network show that LOPC is a metastable structure produced during the transformation from fullerene-type to graphene-type carbons. At a lower temperature, shorter annealing time or by using less α-Li₃N, a well-known polymerized C₆₀ crystal forms owing to the electron transfer from α-Li₃N to C₆₀. The carbon K-edge near-edge X-ray absorption fine structure shows a higher degree of delocalization of electrons in LOPC than in C₆₀(s). The electrical conductivity is 1.17 × 10⁻² S cm⁻¹ at room temperature, and conduction at T < 30 K appears to result from a combination of metallic-like transport over short distances punctuated by carrier hopping. The preparation of LOPC enables the discovery of other crystalline carbons starting from C₆₀(s).