A novel charge transfer complex based on D6h-symmetric coronene and D3h-symmetric 1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile (HAT(CN)6) with 2:1 stoichiometry has been prepared by cosublimation method. We have conducted the measurement of charge transfer and charge transport properties as well as the theoretical calculation. The optical spectra indicate coronene-HAT(CN)6 a charge transfer complex in neutral state. This complex demonstrates typical features of a p-type organic semiconductor and the highest hole field-effect mobility is calculated to be 5.6 × 10−3 cm2 v−1 s−1. Combined with the electronic band structure and intermolecular electronic coupling obtained from corresponding calculation, this research provides assistance in investigating structure-performance relationship and suggests a guideline for developing high-performance binary composed materials. Display omitted •A novel charge transfer complex based on coronene and HAT(CN)6 with 2:1 stoichiometry has been prepared.•The highest hole field-effect mobility is calculated to be 5.6×10-3 cm2 v-1 s-1.•Theory calculations confirm experiment results, suggesting a guideline for studying structure-performance relationship.