Four acetate-decorated tri-Ln-substituted trimeric antimonotungstates (AMTs) Na-17{(WO4)[Ln(H2O)(Ac)(B-alpha-SbW9O31(OH)(2))](3)}center dot 5OH(2)O [Ln = Eu3+ (1), Dy3+ (2), Ho3+ (3), or Gd3+ (4)] were isolated by reaction of Na-9[B-alpha-SbW9O33]center dot 19.5H(2)O, Na2WO4 center dot 2H(2)O, and Ln(NO3)center dot 6H(2)O in a HAc/NaAc buffer solution. Interestingly, a tetrahedral {WO4} group plays a significant structure-directing template role in the formation of their polyoxoanions. With regard to luminescence properties, with a change in the excitation wavelength, it is available to switch emission colors from orange to red for 1, blue to green for 2, and blue to yellow for 3. Under the O -> W LMCT excitation, energy transfer from AMT fragments to Eu3+, Dy3+, and Ho3+ ions occurs because Ln(3+) ions can absorb energy from O -> W LMCT emission of AMT segments. The temperature-dependent lumines- cence behaviors (25-720 degrees C) of 1 together with auxiliary emitting photographs illustrate that the growing emission in the temperature range of 25-100 degrees C results from the loss of lattice water molecules, the decline of emission between 100 and 320 degrees C may occur because crystals become amorphous powders, the slow emission decay (220-320 degrees C) is due to the case that the emission enhancement derived from the removal of water ligands on Eu3+ ions in some degree compensates for the decline of emission intensity, the sharp decrease in emission (320-520 degrees C) may result from the change in the coordinate environment of Eu(3+)ions, and the weak recovery of emission (620-720 degrees C) may be ascribed to the formation of new phase Na0.5Eu0.5WO4. This work lays a significant foundation for preparing novel POM-based luminescent materials.