We present new stilbazolium salt DSTMS (4-N,N-dimethylamino-4′-N′-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate) with both high second-order nonlinear optical properties and very favorable crystal growth characteristics. We are able to obtain very large area bulk single crystals of more than 3 × 3 × 0.2 cm3 with a high optical quality without using seed crystals by using low-temperature solution growth. We also demonstrate the growth of single crystalline thin films of DSTMS with an area of up to 6 × 5 mm2 and a thickness between 5–30 μm. Nonlinear optical measurements reveal that DSTMS possesses large nonlinear optical susceptibilities with χ111(2) = (430 ± 40) pm V–1 at 1.9 μm. Highly efficient generation of broadband THz waves with THz electric field strengths of more than 4 kV cm–1 using 160 fs laser pump pulses at a wavelength λ = 1.45 μm and DSTMS crystals has been demonstrated.