The photoelectrochemical behavior of two polymers of the polythiophene series containing electron-acceptor groups in the main chain was studied and compared to that of the nonmodified polymer, poly(2,2'-bithiophene), PBT. The acceptor groups were 2,2'-bipyridine and biphenyl, which are electron-deficient as compared to the bithiophene unit. All three polymers demonstrated a pronounced photovoltaic effect, which for PBT was consistent with data reported earlier. The introduction of the electron-acceptor moieties was found to significantly enhance the magnitude of the steady-state photocurrent as well as to drastically alter the dependencies of the photocurrent on the polymer film thickness and the external bias. These observations indicated that the mechanism of photocurrent generation in the modified polymers differs from that in nonmodified polymer and involves the electron transfer to the electron-acceptor moieties in the polymer main chain. The values of the external quantum efficiency were estimated in a liquid-cell arrangement to be 0.27 and 0.19% for modified and nonmodified polymers, respectively.