The effect of the preparation and treatment conditions on the photoefficiency of electropolymerized polybithiophene (PBT) was studied. It was found that, after initial discharging, further electrochemical undoping of the polymer in dark had no effect on the photocurrents. However, illuminating the polymer films in solutions containing Li' ions resulted in a five-fold increase in the photocurrent. This fact was attributed to photoelectrochemical removal of the trapped charge that was present in the as-grown polymer films. This conclusion was confirmed by local conductivity measurements using current-sensing atomic force microscopy (CS-AFM). The as-grown polymer films showed a high degree of microscopic heterogeneity and well-pronounced conducting domains of submicrometer dimensions embedded into a nominally undoped polymer phase. Further, electrochemical undoping in dark failed to produce any noticeable change in the trapped charge content. The photoelectrochemical treatment, however, drastically improved the microscopic homogeneity of the polymer and its semiconductor properties, as indicated by CS-AFM images and current-voltage characteristics. The maximum steady-state photocun-ent obtained in LiPF6 was 1.4mAcm-2 under 20 mW 405 nm monochromatic laser illumination, which corresponded to an external quantum efficiency of 1.5%. This result indicates that, upon necessary optimization, single-layer polymer photoelectrodes can produce relatively high photocurrents without employing the donor-acceptor architectures. (c) 2007 Elsevier Ltd. All rights reserved.