Two new dialkylammonium thiosulfates, namely bis(diisopropylammonium) thiosulfate, 2C(6)H(16)N(+)·S(2)O(3)(2-), (I), and bis(tert-butylammonium) thiosulfate, 2C(4)H(12)N(+)·S(2)O(3)(2-), (II), have been characterized. The secondary ammonium salt (I) crystallizes with Z = 4, while the primary ammonium salt (II), with more hydrogen-bond donors, crystallizes with Z = 8 and a noncrystallographic centre of inversion. In both salts, the organic cations and thiosulfate anions are linked within extensive N-H···O and N-H···S hydrogen-bond networks, forming extended two-dimensional layers. Layers are parallel to (101) in (I) and to (002) in (II), and have a polar interior and a nonpolar hydrocarbon exterior. The layered structure and hydrogen-bond motifs observed in (I) and (II) are similar to those in related ammonium sulfates.