6,6',13,13'-Tetrahydro-6,6'-bipentacene (HBP), the intermediate molecule connecting pentacene to previously observed peripentacene and extended pentacene oligomers through the formation of a carbon-carbon bond, is synthesized and crystallographically characterized. Heating pentacene to 300 °C under vacuum for 200 h results in pale golden crystals of HBP and amorphous material containing pentacene oligomers, offering experimental evidence that pentacene preferentially dimerizes at the 6,6'-position. Continued heating of HBP results in co-crystals of 6,13-dihydrogenated pentacene and pentacene and further amorphous pentacene oligomers. The amorphous material consists of layered carbonaceous species with a graphenic nature, as determined by Raman spectroscopy and electron microscopy, and suggests HBP as an intermediate to hydrogenated pentacene species and pentacene oligomers, such as peripentacene, of interest in organic electronics.