A new complex [Pb(Crypt-222)(H2O)2]+ · 2(iso-PrO)2P(S)N−C(S)Ph (I) was prepared and studied by X-ray diffraction: space group C2/c, a = 16.170 A, b = 10.405 A, c = 34.116 A, β = 103.32°, Z = 4. The monoclinic structure of I was solved by direct methods and refined by full-matrix least-squares calculation in the anisotropic approximation to R = 0.098 for 6414 independent reflections (CAD4 automated diffractometer, λMoKα). In structure I, the host-guest [Pb(Crypt-222)(H2O)2]+ cation is located on a twofold crystallographic axis. The Pb2+ cation is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand and by two O atoms of water molecules. The Pb2+ coordination polyhedron (CN = 10) is a highly distorted two-base-centered dicapped trigonal prism. The crystal structure of I contains one independent thiophosphoramidate anion with deprotonated nitrogen. In crystal I, the complex cation is connected to two thiophosphoramidate anions by ion-ion hydrogen bonds, O(w)-H...S.