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Abstract We describe two component hydrogels with networks composed of self-sorted fibres. The component gelators are based on 1,4-distyrylbenzene (OPV3) and perylene bisimide (PBI) units. Self-sorted gels can be formed by a slow decrease in pH, which leads to sequential assembly. We demonstrate self-sorting by NMR, rheology and small angle X-ray scattering (SAXS). Photoconductive xerogels can be prepared by drying these gels. The wavelength response of the xerogel is different to that of the PBI alone.