The molecular structure of NaI. N(CH2CH2OCH3)3(2,2‘,2“‐trimethoxytriethylamine‐sodium iodide complex) has been established by a three‐dimensional single‐crystal X‐ray analysis. The crystals are orthorhombic, space groupPna21with one molecule per asymmetric unit anda= 14.777 (9),b= 7.560 (3),c= 13.570 (3) Å. The structure was solved by the heavy‐atom method from data collected at room temperature on a four‐circle diffractometer using the θ‐2θ scan technique. It was refined by the least‐squares method toR= 0.034 for 1173 observed reflexions. The structure of the five‐coordinated complex of sodium is described and discussed. The crystal structure consists of discrete molecules in which the sodium cation is pentacoordinated. Each sodium atom is bonded to all heteroatoms of one ligand and to the iodine ion. The Na‐N distance is 2.46 Å. The mean value of the Na‐O distances is 2.35