The relationship between the crystal structures, band structures, and electronic properties of acene−TCNQ complexes has been investigated. We focus on the newly synthesized crystals of the charge-transfer salt tetracene−TCNQ and similar to it perylene−TCNQ, potentially interesting for realization of ambipolar transport. The band structures were calculated from first principles using density-functional theory (DFT). Despite the similarity in the crystal structures of the acene−TCNQ complexes studied here, the band structures are very different. Hole and electron transport properties are predicted to be equally good in perylene−TCNQ, in contrast to the tetracene−TCNQ, which has good transport properties for electrons only. The estimated degree of charge transfer for tetracene−TCNQ is 0.13e and for perylene−TCNQ 0.46e.