Ultrahigh-mobility organic field-effect transistors (OFETs) based on a CDT-BTZ donor-acceptor copolymer are realized by reaching high molecular order and pronounced alignment in single fibers within a short OFET channel via solution processing. The macromolecules directionally self-assemble in a quasi crystal-like order in the fibers providing in this way an unhindered charge carrier pathway with mobilities as high as 5.5 cm(2) V(-1) s(-1).