Two new rubidium iodates, namely, beta-RbIO3(HIO3)(2) (1, P1) and Rb-3(IO3)(3)(I(2)O5)(HIO3)(4)(H2O) (2, P21/c), have been synthesized by hydrothermal reaction and their structures determined by single-crystal X-ray diffraction. Compound 1 exhibits IO3- anions and neutral HIO3 molecules which are interconnected by Rb+ cations into three-dimensional structure. Compound 2 features a two-dimensional layered structure formed by IO3 anions and neutral HIO3 and dimeric I2O5 molecules interconnected by Rb+ cations. Large bulk crystal of 1 with dimensions of several millimeters has been grown. UV-vis-NIR transmission spectroscopy measurements on a slab of a polished crystal of 1 indicated that the crystal possesses a short-wavelength absorption edge onset at 305 nm. Powder second-harmonic generation (SHG) measurements on sieved crystals revealed that 1 is a type I phase-matchable material with an SHG response about 1.5 times that of KH(2)PO4. The Vickers hardness of crystal of 1 has been measured to be 110 HV, and the laser-induced damage threshold has been confirmed to be 18.26 J/cm(2) with a laser wavelength of 1064 nm and a pulse duration of 10 ns. Moreover, thermal stabilities and vibrational spectra for both 1 and 2 have also been studied.