Three rare-earth containing docosatungstates Na3H2[RE(H2O)(4)][RE(H2O)(5)](2)[W22O74H2]center dot 36H(2)O [RE = DYIII(1), Ho-III (2), Y-llI (3)] have been synthesized by reaction of Na2WO4 center dot 2H(2)O, dimethylamine hydrochloride (DMAHC) and RE(NO3)(3)center dot 6H(2)O in the aqueous solution and characterized by elemental analyses, IR spectra, thermogravimetric (TG) analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. 1-3 are isomorphous and each molecular unit consists of a S-shaped docosatungstate [W22O74H2](14-) polyoxoanion with two supporting [RE(H2O)(5)](3+) cations and one disordered IRE(H2O)(4)](3+) cation. The [W22O74H2](14-) polyoxoanion can be viewed as combination of two hendecatungstate [W11O38H](9-) subunits in the staggered fashion by sharing two mu(2)-O atoms. The TG curves of 1-3 reveal the one-step weight loss between 25 degrees C to 700 degrees C. Moreover, both 1 and 2 demonstrate the characteristic luminescence emission behaviors of the corresponding RE3+ ions and their lifetime decay curves can be well fitted to the double exponential function. In addition, the CIE chromaticity coordinates of 1 and 2 have been obtained based on their corresponding emission spectra, and their dominant wavelengths and color purities have been also calculated. (C) 2017 Elsevier B.V. All rights reserved.