This lecture focuses on the challenging design and realization of new materials for creating unconventional electronic circuitry to achieve functions not possible with conventional electronic materials, such as large-area coverage, optical transparency, and mechanical flexibility. Fabrication methodologies to achieve these goals include high-throughput, large-area printing techniques. Materials design topics to be discussed in this lecture include: (1) rationally designed high-mobility p- and n-type organic semiconductors for printed organic CMOS, (2) self-assembled and printable high-k nanodielectrics enabling ultra-large capacitance, low leakage, high breakdown fields, minimal trapped interfacial charge, and device radiation hardness, (3) polycrystalline and amorphous oxide semiconductors for transparent and mechanically flexible electronics, and (4) combining these materials sets to fabricate a variety of high-performance thin-film transistor-based devices.