Azaboradibenzo[6]helicene, a new semiconductor material possessing helical chirality, has been synthesized via a tandem bora-Friedel-Crafts-type reaction. Unprecedented carrier inversion between the racemate (displaying p-type semiconductivity) and the single enantiomer (displaying n-type semiconductivity) was observed and can be explained by changes in the molecular packing induced by helical homochirality.