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Conventional polymer additives have a substantial impact on synthetic inorganic chemistry, but critical shortcomings remain; for example, low solubility in organic solvents and potential thermodynamic aggregates. Poly(ionic liquid)s have now been used as efficient additives that enable a high level control of bismuth sulfide crystals with significant size and morphological diversities. The bismuth sulfides exhibit tunable band structure as a result of the quantum size effects. Moreover, poly(ionic liquid)s are able to couple with as-synthesized bismuth sulfides chemically and endow a modified surface electronic structure, which allows resultant products to possess outstanding electrocatalytic performance for water oxidation, although its commercial counterpart is catalytically inert. [ABSTRACT FROM AUTHOR]