We report on the crystal growth, linear and nonlinear optical properties of LiNa 5 Mo 9 O 30 . The refractive indices were measured, and a very large birefringence of 0.2545 at 450.2 nm was determined. In addition, calculated phase-matching curves indicate that LiNa 5 Mo 9 O 30 can achieve non-critical type I and type II phase-matching (NCPM) for incident 1064nm radiation. Maker-fringe measurements, to determine individual non-linear optical coefficients, were also performed on the crystals in d 31 = 1.4 pm/V, d 32 = 4.3 pm/V, and d 33 = 1.1 pm/V. The laser damage threshold (LDT) is around 1.2 GW/cm 2 at 1064 nm using a 6 ns Nd:YAG laser operating at 5The quality of the crystals were measured by high resolution x-ray diffraction rocking curve measurements that revealed a full width at half maximum (FWHM) of 59'' from the (001) reflection. The absorption edge was determined to be 357 nm, with transmission up to 5.26 µm. Our results indicate that single crystal LiNa 5 Mo 9 O 30 is an excellent polarizer as well as second-order nonlinear optical material.