Quantum chemical calculations have predicted the existence of a new carbon family with double-layered structures formed by arranging prism-C2n (n = 6, 8, and 12) units. Theoretical explorations of potential energy surfaces suggest the lowest barriers of the reaction channels to be ca. 30 kJ mol−1 for a D2h prism-C16 dimer and a D3h prism-C24 trimer. Geometry optimizations under periodic boundary conditions yield some prism-C2n sheets composed of CC single bonds of ca. 0.15–0.16 nm. The relative energies per one atom with respect to graphene are 90–160 kJ mol−1. Van der Waals thickness is estimated to be ca. 0.5 nm.