The microstructure and charge transport properties of binary blends of regioregular (rr) and regiorandom (RRa) poly(3-hexylthiophene) (P3HT) are investigated. X-ray diffraction of the blended films is consistent with a vertically separated structure, with rr-P3HT preferentially crystallizing at the semiconductor/dielectric interface. Thin film transistors made with these blended films preserve high field effect mobility with rr-P3HTcontent as low as 5.6%. In these dilute blends, we estimate that the thickness of rr-P3HT in the channel is only a few nanometers. Significantly, as a result of such an ultrathin active layer at the interface, short channel effects due to bulk currents are eliminated, suggesting a new route to fabricate high-performance, short-channel, and reliable organic electronic devices. © 2013 American Chemical Society.