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Charge carrier transport in pure and phenylated poly(naphthoylenebenzimidazole) was compared by measurements of transient radiation-induced conductivity. Irradiation with single 100-μs pulses of 55-keV electrons was carried out in vacuum at room temperature. Contrary to expectations, the phenylation deteriorated the transport properties of a polymer: the delayed radiation-induced conductivity in phenylated poly(naphthoylenebenzimidazole) was almost 50 times lower than in the initial polymer, with the dispersion parameter decreasing from 0.4-0.25 to ≤0.05. As a result, the drift mobility of charge carriers falls by a few orders of magnitude. The mechanism of such behavior still remains unclear.