A crystalline mixed-metal sulfate compound NaPr(SO4)2(H2O) is synthesized under hydrothermal conditions and thoroughly characterized. Sodium bisulfite (NaHSO3) and piperazine are used with praseodymium acetate to obtain this sulfate-based structure. The single crystal structural analysis shows that the compound has the NaCe(SO4)2 · H2O structure type and crystallizes in the trigonal space group P3221 (No. 154) with a = 6.9872(2) Å, c = 12.8935(8) Å, and V = 545.14(4) Å3. The compound has three-dimensional connectivity formed by the sulfate units with Pr and Na centers. Tricapped trigonal prismatic PrO9 units and square-antiprismatic NaO8 units link to the SO4 tetrahedron for building the three-dimensional structure. The compound is also characterized by PXRD, TGA, and FT-IR spectroscopy. The present study illustrates the usefulness of the bisulfite anion and secondary amine for the chiral structure building.