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The formation of high-concentration mesophases by a cationic azobenzene photosurfactant is described for the first time. Using a combination of polarised optical microscopy and small-angle X-ray scattering, optically anisotropic, self-assembled structures with long-range order are reported. The mesophases are disrupted or lost upon UV irradiation.Due to an increasing requirement of clean and sustainable hydrogen energy economy, it is significant to develop new highly effective catalysts for electrochemical water splitting. In alkaline e