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Herein, we have developed a facile and general route for high-yield fabrication of single-crystalline Ag3PO4 rhombic dodecahedrons exposed totally with { 110 } facets and cubes bounded entirely by { 100 } facets.Moreover, their photocatalytic performance studies indicate that nhombic dodecahedrons exhibit much higher activities than cubes for the degradation of organic contaminants, which /may be primarily ascribed to higher surface energy of {110} facets (1.31 J/m2) than that of {100} facets (1.12 J/m2).