A new class of polyphospholes bearing alkanesulfonylimino moieties on the phosphorus(V) centers was prepared by the Pd-CuI-promoted Stille coupling reaction to investigate the charge-carrier transport properties of the π-networks of polyphospholes. Time-of-flight measurements have revealed that the poly(phosphole P-imide)s possess ambipolar charge-carrier mobilities of up to μ(electron) = 6 × 10(-3) cm(2) V(-1) s(-1) and μ(hole) = 4 × 10(-3) cm(2) V(-1) s(-1).