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Ga-soc-MOF hollow cubes with an average size of about 300 nm were prepared by a polyvinylpyrrolidone (PVP) assisted acid etching process. Colloidosomes with sizes of around 5-10 μm composed of single-layer tetrakaidecahedron building blocks (BBs) were synthesized for the first time. Au@Ga-soc-MOF nanocomposites with excellent catalytic properties were obtained.