We report the experimental and computational study of a cyclopenta-fused polycyclic aromatic hydrocarbon molecule TPCPA. Using naphthalene flux method, we succeeded in the single crystal growth and found two different polymorphs. One is herring-bone type (Type 1), and another is a layered structure consisting of alternative stacking of pitched-p stack and brick-work structure (Type 2). From computational analysis, it is predicted that Type 1 is an one-dimensional n-type semiconductor, and Type 2 is a two-dimensional ambipolar semiconductor. The difference comes from the special distribution and the symmetry of the frontier orbitals. Applications for near infrared and ambipolar devices are expected.