Single crystals of two uranium silicates, Cs(2)USi0(6) and Rb(2)USi0(6), have been grown from molten fluoride fluxes and structurally characterized by single-crystal X-ray diffraction. Cs(2)USi0(6) crystallizes in the body-centered orthorhombic space group, Immm, with a = 8.5812(4) A, b = 13.0011(6) A, and c = 13.8811(7) A. The size of Rb is slightly too small to fit into this structural framework without effecting slight structural changes that result in a 6-fold superstructure. Sharp satellite peaks were observed in the single-crystal X-ray diffraction data, indicating the existing of a superstructure. The crystals were examined by electron diffraction, the results of which suggest that the structure can be thought of as the Immm isotype (a = 8.4916(6) A, b = 12.6678(9) A, and c = 13.5077(9) A) on average, with an approximately 6-fold superstructure along the c axis. The materials were further characterized by UV-vis reflectance spectroscopy.