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 two benzoates coordinating to the Ln3+ ions. 1-3 exhibit reversible photochromism, which can change from intrinsic white to blue for 6 min upon UV irradiation, and their colors gradually recover for 30 h in the dark. The solid-state photoluminescence spectra of 1 and 2 display characteristic emissions of Ln components based on 4f-4f transitions. Time-resolved emission spectra of 1 and 2 were also measured to authenticate the energy transfer from the phosphotungstate and organic chromophores to Eu3+. In particular, 1 shows an effectively switchable luminescence behavior induced by its fast photochromism.