A facile, dextran-directed solution route for the morphology- and structure-controlled synthesis of PbWO(4) crystals, such as monoclinic raspite PbWO(4) nanobelts and tetragonal stolzite PbWO(4) crystals with penniform and wheat-ear-like morphologies, has been demonstrated. Three differently charged dextrans were employed for the PbWO(4) crystallization and they turned out to be very effective in the morphological and structural modulation of PbWO(4) crystals, as evidenced by the scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD) and Raman spectroscopy characterizations. In particular, novel monoclinic raspite PbWO(4) nanobelts were produced under the direction of anionic dextran with a suitable concentration, probably due to the specific interactions between SO(4)(2-) groups from anionic dextran molecules and Pb(2+) ions from PbWO(4) crystals. To the best of our knowledge, this is the first synthesis of monoclinic raspite PbWO(4) in the laboratory, which usually exists as a natural crystal. In addition, the photoluminescence properties of the obtained PbWO(4) crystals with different morphologies and crystal structures have been characterized and discussed, which provides useful information for the fundamental investigation and potential application of PbWO(4) crystals.