In the crystal structure of the title compound, C(6)H(16)N(+)·C(34)H(52)O(2)PS(2) (-) or [(CH(3)CH(2))(3)NH](+)·[C(34)H(52)O(2)PS(2)](-), the cation and anion are paired via weak, inter-molecular, bifurcated N-H⋯(S,S) hydrogen bonds. The cholesteryl units form an alternating (herringbone) motif as well as an infinitely stacked layered structure along the b axis. The P-S bond lengths [1.975 (2) and 1.981 (2) Å compared with ca 1.92 Å for a formal P=S double bond and with ca 2.01 Å for a P-S single bond] suggest delocalization of the negative charge between the P-S bonds. A distorted tetra-hedral geometry around the P atom is revealed by non-ideal O-P-C and S-P-S bond angles of 96.7 (2) and 115.52 (11)°, respectively.