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A series of benzoate-decorated lanthanide (Ln)-containing tetrameric Dawson-type phosphotungstates [N(CH3)4]6H20[(P2W17O61)Ln(H2O)3Ln(C6H5COO)(H2O)6][(P2W17O61)Ln(H2O)3]2Cl2·98H2O [Ln = Sm (1), Eu (2), and Gd (3)] were made using a facile one-step assembly strategy and characterized by several techniques. Notably, the Ln-containing tetrameric Dawson-type polyoxoanions [(P2W17O61)Ln(H2O)3Ln(C6H5COO)(H2O)6][(P2W17O61)Ln(H2O)3]224- are all established by four monolacunary Dawson-type [P2W17O61]10- segments, encapsulating a Ln3+ ion with tw