In this study, we demonstrate, for the first time, that SOSIP, self-organizing surface-initiated polymerization, a method introduced for facile access to complex surface architectures, is compatible with perylenediimides (PDIs), i.e., established chromophores with very important properties. Highly ordered face-to-face π-stacks are shown to coincide with a more than 100-fold increase of the activity of PDI photosystems, and with significant fill factors. This breakthrough with electron-transporting PDI stacks promises access to powerful combinations with hole-transporting channels.