We developed a new donor--acceptor-type hole-transport material (HTMs) incorporating S,N-heteropentacene as -spacer, triarylamine as donor, and dicyanovinylene as acceptor. In addition to appropriate frontier molecular orbital energies, the new HTM showed high photo absorptivity in the visible region. Without the use of p-dopants, solution-processed mixed perovskite devices using the HTM achieved power conversion efficiencies of up to 16.9% and high photocurrents of up to 22.2mAcm(-2). These results demonstrate that heteroacene can be an excellent building block to prepare alternative HTMs for perovskite solar cells and hold promise for further advancement through fine-tuning the molecular structure.