The synthesis of a new calcium complex based on biologically active ligands with N and O donor atoms is an attractive research topic in modern synthetic chemistry. Herein we present the formation of AB2- type salt [Ca(TEA) ₂ ](4NB) ₂ (1) by an easy method, starting from CaF ₂ , 4-nitrobenzoic acid (4NBH) and triethanolamine (TEA). The crystal structure comprises one [Ca(TEA) ₂ ] ²⁺ complex cation and two 4NB- anions. In the complex cation, each TEA molecule behaves as an N,O,O',O'-tetradentate ligand, giving rise to an eight-coordinate Ca(II) ion with a distorted cubic configuration. The complex cation is H-bonded with outer-sphere 4NB- anions by intermolecular O-H O hydrogen bond interactions. The intermolecular O-H O hydrogen bonds unite components in well-defined 1D supramolecular chain, which are further assembled in a supramolecular 2D layer via π- π stacking interactions.