Regular WO3 nanocubes have been prepared on a large scale through a convenient hydrothermal route at the temperature of 200 °C. The products were characterized by powder X-ray diffraction (XRD), field-emission scanning electron microscopy, UV-vis diffuse reflectance spectroscopy (DRS), and photoluminescence (PL) spectroscopy. A crystal growth process for WO3 nanocubes was simply proposed based on the comparative experiments. The band gap energy (Eg) was determined to be 2.58 eV based on the UV-vis DRS analysis, and the PL spectrum exhibited a strong blue light emission band centered at 469 nm. The as-prepared WO3 nanocubes showed higher visible light photocatalytic performance for degrading rhodamine B compared with WO3·H2O and WO3·0.33H2O/WO3 which were obtained at 80 °C and 140 °C, respectively, suggesting potential application in the region of wastewater purification.