In the title compound, [Na2(N3)2(C21H34N2O6)2] 2CHCl3, the sodium cation is heptacoordinated by five O atoms of the crown ether unit of the 1-hexyl-3-(2,3,5,6,8,9,11,12-octahydro- 1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)urea (L) ligand, the O atom of the urea group of the second, symmetry-related L ligand, and one N atom of the azide anion. The experimentally determined distance 2.472 (2) A ˚ between the terminal azide N atom and the sodium cation is substantially longer than that predicted from density functional theory (DFT) calculations (2.263 A ˚ ). The crown ethers complexing the sodium cation are related by an inversion centre and form dimers. The urea groups of the two L ligands are connected in a head-to-tail fashion by classical N--H...N hydrogen-bonding interactions and form a ribbon-like structure parallel to the b axis. Parallel ribbons are weakly linked through C--H...N, C--H...O and C--H...pi interactions.