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We report the synthesis and characterization of perfluoropentacene as an n-type semiconductor for organic field-effect transistors (OFETs). Perfluoropentacene is a planar and crystalline material that adopts a herringbone structure as observed for pentacene. OFETs with perfluoropentacene were constructed using top-contact geometry, and an electron mobility of 0.11 cm² V^-1 s^-1 was observed. Bipolar OFETs with perfluoropentacene and pentacene function at both negative and positive gate voltages. The improved p−n junctions are probably due to the similar d-spacings of both acenes. Complementary inverter circuits were fabricated, and the transfer characteristics exhibit a sharp inversion of the output signal with a high-voltage gain.