Introduction of pentagonal units into carbon-based materials is of considerable interest to perturb the geometric and electronic properties of the original structures composed of only hexagonal rings. We succeeded in the synthesis of a dibenzopentalene-linking polymer through C-C bonds between the pentagonal carbon atoms from 5,10-dibromodibenzopentalene under the two-zone chemical vapor deposition (2Z-CVD) and wet conditions. The resulting polymer was characterized by Raman spectroscopy. The present finding would spotlight the polymerization of a compound containing pentagonal moieties to introduce pentagonal units into carbon materials.