We report the fabrication of triisopropylsilyl (TIPS)–pentacene-based thin-film transistors (TFTs) consisting of a nickel oxide–indium tin oxide (NIO–ITO) multi stacked source/drain (S/D) electrode, a poly(4-vinylphenol) (PVP) gate dielectric, and a Ni gate electrode. The NiO–ITO multi stacked S/D electrode work function agrees well with to that of the TIPS–pentacene active channel layer. The TIPS–pentacene-based TFT maximum saturation current is about 9.1 µA at a gate bias of -40 V, representing a high field effect mobility of 0.03 cm2 V-1 s-1 in the dark, and the on/off current ratio TFT is about 105. We concluded that combining the NiO–ITO multi stacked S/D electrodes with PVP for the gate dielectric yields a high-quality TIPS–pentacene-based TFT.