A new calcium(II) complex of the saccharinate ligand (sac) with 2-hydroxyethylpyridinium (Hpyet) was synthesized and characterized by elemental analysis, FT-IR spectroscopy, thermal analysis and single crystal X-ray diffractometry. The [Ca(sac)(2)(H2O)(2)(Hpyet)(2)](sac)(2) complex crystallizes in the triclinic space group (P (1) over bar) with the cell dimensions a = 7.4360(7) Angstrom, b = 12.5263(12) Angstrom, c = 12.8329(13) Angstrom, alpha = 82.534(8)degrees, beta = 75.202(8)degrees and gamma = 89.662(8)degrees (293 K). The title complex consists of a complex cation and two sac anions. In the complex cation, the calcium(II) ion is six-coordinate, bonding to two aqua ligands, two Hpyet ligands andtwo sac ligands located in the trans positions. Two of the sac ions are coordinated to the calcium(II) ion through the carbonyl 0 atom, while the other two remain outside the coordination sphere as the counter-ions. Thermal decomposition of the complex in air results in elimination of aqua, Hpyet, and sac ions, respectively.