A facile, dextran-directed solution route for the morphology- and structure-controlled synthesis of PbWO₄ crystals, such as monoclinic raspite PbWO₄ nanobelts and tetragonal stolzite PbWO₄ crystals with penniform and wheat-ear-like morphologies, has been demonstrated. Three differently charged dextrans were employed for the PbWO₄ crystallization and they turned out to be very effective in the morphological and structural modulation of PbWO₄ 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 PbWO₄ nanobelts were produced under the direction of anionic dextran with a suitable concentration, probably due to the specific interactions between SO₄²⁻ groups from anionic dextran molecules and Pb²⁺ ions from PbWO₄ crystals. To the best of our knowledge, this is the first synthesis of monoclinic raspite PbWO₄ in the laboratory, which usually exists as a natural crystal. In addition, the photoluminescence properties of the obtained PbWO₄ crystals with different morphologies and crystal structures have been characterized and discussed, which provides useful information for the fundamental investigation and potential application of PbWO₄ crystals.