ACS Nano – Molecularly hybridized materials composed of polymer semiconductors (PSCs) and single-walled carbon nanotubes (SWNTs) may provide a new way to exploit an advantageous combination of semiconductors, which yields electrical properties that are not available in a single-component system. We demonstrate for the first time high-performance inkjet-printed hybrid thin film transistors with an electrically engineered heterostructure by using specially designed PSCs and semiconducting SWNTs (sc-SWNTs) whose system achieved a high mobility of 0.23 cm2 V–1 s–1, no Von shift, and a low off-current. PSCs were designed by calculation of the density of states of the backbone structure, which was related to charge transfer. The sc-SWNTs were prepared by a single cascade of the density-induced separation method. We also revealed that the binding energy between PSCs and sc-SWNTs was strongly affected by the side-chain length of PSCs, leading to the formation of a homogeneous nanohybrid film. The understanding of electrostatic interactions in the heterostructure and experimental results suggests criteria for the design of nanohybrid heterostructures.