Nanomaterials with both superhydrophobic surface properties as well as photocatalytic activities could have important industrial applications. Herein, we synthesized CeVO4 nanocrystals with hexagonal nanoplate structures from the reaction of decavanadate (K6V10O28⋅9 H2O) and CeCl3⋅H2O precursors via a hydrothermal method. This synthetic route has four advantages: 1) the reaction condition is relatively mild, 2) it doesn′t need surfactants or templates, 3) it requires no expensive equipment, and 4) products are of higher purity. During synthesis, solution pH, and reaction temperature were found to play important roles in determining the growth process and final morphologies of the CeVO4 products. These products were characterized spectrophotometrically and via scanning and transmission electron microscopy. Furthermore, the wettability of the as-synthesized film CeVO4 nanoplates was studied by measuring water contact angle (CA). The largest CA measured was at 169.5 ° for a glass substrate treated with 0.06 g mL−1 CeVO4 followed by 2 % 1 H, 1 H, 2 H, 2 H-perfluorodecyltriethoxysilane. Finally, the CeVO4 nanoplates exhibited excellent photocatalytic activity in degradation of rhodamine B (RhB) under UV irradiation and was stable even after repeated cycles of use.