In this paper, various microstructures of yttrium and lanthanum tungstates were synthesized under hydrothermal conditions, at pH 5, in a ligand-free environment, and in the presence of a dioctyl sodium sulfosuccinate (DSS) surfactant. It was observed that the shape of the nanobuilding blocks, and therefore the architecture of the microstructures, could be tuned by controlling the reaction conditions, such as the source of the rare earth, the amount of a surfactant and the reaction time. X-ray powder diffraction (XRD), elemental analysis, scanning electron microscopy (SEM), and N2 adsorption were employed to characterize the obtained products. The photoluminescent properties of Eu(3+) and Dy(3+) doped tungstate materials were investigated. Luminescence measurements showed an efficient charge transfer from the WO4(2-) groups to Eu(3+) and Dy(3+) ions. It was found that under UV excitation the Dy(3+) doped Y(WO3)2(OH)3 and La2(WO4)3 precursors exhibit white emission.