A novel strategy for constructing a vertical arrangement of bicontinuous donor-acceptor arrays on a semiconducting electrode has been developed. The relationship between the film structure and the photoelectrochemical properties has been elucidated as a function of the number of donor Layers for the first time. The maximum incident photon-to-current efficiency value (21%) is comparable to the highest value (20%) reported for vertical arrangements of bicontinuous donor-acceptor arrays on electrodes.