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In the crystal of the title salt, C6H9N2O2S+·ClO4−, the components are linked by N—H...O hydrogen bonds, forming a three-dimensional network. The cations are connected along a and b axes, leading to linear and zigzag C(3) and C(8) chain motifs, respectively. A cation–anion interaction along the c axis leads to a C22(12) chain motif. R33(18) and R33(20) ring motifs are observed as cation–anion-type interactions. These hydrogen-bonding ring and chain motifs are localized at z = 0 or 1, leading to alternate hydrophilic and hydrophobic regions along the c axis as a result of the stacking of anions and the aromatic cationic parts.