The reaction of the deprotonated N‐thiophosphorylated bisthiourea N,N′‐bis(diisopropoxythiophosphorylamidothiocarbonyl)hydrazine {[NHC(S)NHP(S)(OiPr)2]2, H2L} with ZnCl2 leads to the complex [Zn2{[NHC(S)NP(S)(OiPr)2]2}2] ([Zn2L2]), in which two metal cations are each 1,5‐S,S′‐coordinated through the sulfur atoms of the thiocarbonyl and thiophosphoryl groups of the pendant deprotonated thioacylamidothiophosphate functions. The same reaction with CdCl2 leads to the tetranuclear nanoscaled aggregate [(Cd2{[NC(S)NHP(S)(OiPr)2]2}2)2] ([(Cd2L2)2]). This complex contains ligands that are doubly deprotonated through their hydrazine NH groups and exhibit unprecedented μ4 and μ5 coordination modes. DFT calculations have shown that both complexes are stabilized not only by typical coordination bonds (Zn–S, Cd–S) but also by numerous intramolecular “noncovalent” interactions: polar C–H···S and N–H···S, nonpolar C–H···H–C, and σ‐hole bonding (S···S).