Poly(p-phenylene vinylene) derivatives (PPVs) are one of the most widely investigated p-type polymers in organic electronics. PPVs generally exhibit electron mobilities lower than 10(-4) cm(2) V-1 s(-1), thus hindering their applications in high-performance polymer field-effect transistors and organic photovoltaics. Herein, we design and synthesize a novel electron-deficient PPV derivative, benzo-difurandione-based PPV (BDPPV). This new PPV derivative displays high electron mobilities up to 1.1 cm(2) V-1 s(-1) under ambient conditions (4 orders of magnitude higher than those of other PPVs), because it overcomes common defects in PPVs, such as conformational disorder, weak interchain interaction, and a high LUMO level. BDPPV represents the first polymer that can transport electrons over 1 cm(2) V-1 s(-1) under ambient conditions.