Two picrates of l-cysteine have been obtained, (l-CysH)picrate (I) and l-Cys(l-Cys-½H···½H- l-Cys)picrate (II). The (I) crystallizes in the monoclinic space group P21 and the (II) in the orthorhombic space group P212121. (l-CysH)picrate (I) is a simple salt with l-cysteinium cation, while l-Cys(l-Cys-½H···½H- l-Cys)picrate (II) includes (l-Cys-½H···½H- l-Cys) dimeric cation formed by O–H⋯O hydrogen bonds with O⋯O distance of 2.442(11) Å. Also, there is a l-cysteine zwitterion in the structure. Infrared and Raman spectra were registered. They are discussed in relation to the characteristics of the hydrogen bonds. l-Cysteinium picrate (I) has nonlinear-optical properties. The intensity of second harmonic generation signal is 1.6 times higher than that of KDP.