The title compound, rac-6,13-dihydro-6,13-methanopentacene (1), has been synthesized and characterized by elemental analysis, FT-IR, 1 H NMR, UV-Vis, HRMS spectra, cyclic voltammetry and single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group P2 1 2 1 2 1 , with Z = 4 and cell dimensions a = 6.0185(4), b = 8.1914(6), c = 31.4080(19) Å. In the crystal structure, two types of intermolecular C-H×××p hydrogen bonds are observed, and further stabilize the crystal structure. Its photophysical and electrochemical properties and complementary density functional theory (DFT) calculations are reported.