We report that self-sorting during self-organizing surface-initiated copolymerization (co-SOSIP) provides facile access to oriented multicomponent architectures. Alternate lateral and uniform axial self-sorting into formal supramolecular n/p-heterojunction photosystems is found to generate up to 40 times more photocurrent. More or less topological matching gives rise to alternate axial self-sorting into inactive charge-transfer complexes or uniform lateral sorting into the less active macrodomains, respectively. Experimental support for self-repair during co-SOSIP is reported. Initiators on the surface are shown to serve as templates for the self-sorting into multichannel architectures of freely variable composition.