The bulk LiNa5Mo9O30 (LNM) crystals were successfully grown in the [010] and [001] directions without internal inclusions and cracks by the Czochralskii method with low temperature gradient. The crystal grown in the [010] direction showed a tendency to twinning. The crystal grown in the [001] direction demonstrated high structural perfection (FWHM=13'') for the (001) plane and high optical quality Δn≈210-5. The laser induced damage threshold was measured along a, b and c axes and was 15.7, 27.0 and 27.5 J/cm2 respectively. The thermo-optical coefficient dn/dT was measured for the main crystallographic axes, which was -5.7510-6, -2.0210-5 and 3.6510-6 K-1 along the a, b and c axes, respectively. The second harmonic generation (SHG) is conducted in crystalline LNM sample. The maximum efficiency value of 3.5% at pump power of 12 W had been achieved.