The design, synthesis and nonlinear optical (NLO) response of some bent compounds, at both the molecular and macroscopic level, are reported. Based on a bent-core NLO-phore with a μβ₀ in the range of 390 × 10⁻⁴⁸ esu (1907 nm), the second order susceptibility tensor for second harmonic generation is evaluated at excitation wavelengths of 1064 and 1600 nm in a mesogenic material with a SmCP mesophase. The NLO coefficients are in the range 10–100 pm V⁻¹ . Thus it is deduced that a molecular design leading to bent-core liquid crystals with large β values is a correct strategy to achieve NLO-materials for bulk second order effects.