A new hybrid organic–inorganic non-linear optical crystalline material, L-argininium perrhenate has been synthesized. The crystal belongs to P212121 space group, has a good optical quality and high transmission in the visible and near infra-red spectral regions. L-argininium perrhenate has high birefringence and is more than four times as efficient as KDP in second harmonic generation, making it a potentially attractive material for non-linear optical applications