The photoinduced charge separation and subsequent transport under an external electric field is studied in the family of poly[bipyridine/(p-phenylene-vinylene),] derivatives having n = 0, 1, and 3, respectively, p-phenylenevinylene subunits separating the bipyridylene vinylene, skeleton. Steady-state photocurrent of the polymers is studied in sandwich and surface configurations and correlated with transient photocurrent measurements. The results reveal the facile electric-field-induced separation of the electron-hole pair for n = 1 samples relative to n = 3 samples. We also estimate the energy barriers involved in the process of carrier generation and transport in these systems.