The synthesis and characterization of a series of novel small-molecule holetransporting materials (HTMs) based on an anthra [1,2-b: 4,3-b': 5,6-b '': 8,7-b '''] tetrathiophene (ATT) core are reported. The new compounds follow an easy synthetic route and have no need of expensive purification steps. The novel HTMs are tested in perovskite solar cells and power conversion efficiencies (PCE) of up to 18.1% under 1 sun irradiation are measured. This value is comparable with the 17.8% efficiency obtained using 2,2', 7,7'-tetrakis(N, Ndi- p-methoxyphenylamine)-9,9'-spirobifluorene as a reference compound. Similarly, a significant quenching of the photoluminescence in the first nanosecond is observed, indicative of effective hole transfer. Additionally, the influence of introducing aliphatic alkyl chains acting as solubilizers on the device performance of the ATT molecules is investigated. Replacing the methoxy groups on the triarylamine sites by butoxy-, hexoxy-, or decoxy-substituents greatly improves the solubility of the compounds without changing the energy levels, yet at the same time significantly decreasing the conductivity as well as the PCE, 17.3% for ATT-OBu, 15.7% for ATT-OHex, and 9.7% for ATT-ODec.