In this work, we investigated the photoelectrochemical behavior of poly(4,4 ' -dipentoxy-2,2 ' -bithiophene), poly(ET2), as a single electrode in a liquid electrolyte and also its use in a solid-state photoelectrochemical device using a polymeric electrolyte. The results showed a strong dependence of the photocurrent density on the type and concentration of the redox couple. The solid-state device exhibited a short-circuit current density of 4 muA cm(-2) and an open-circuit voltage of 9 mV. The maximum quantum yield of photocurrent in the visible range was 0.17%, high when compared to other photoelectrochemical devices based on organic materials; however, it is low in comparison to solid-state devices using inorganic materials. This paper shows the viability of using organic polymeric electrolytes in the construction of photoelectrochemical devices,