Reaction of the potassium salts of N-(thio)phosphorylated thioureas of common formula AdNHC(S)N(H)P(X)(OiPr)₂ (Ad = adamantyl; X = O, HL ^I ; X = S, HL ^II ) with Co(II), Zn(II), and Cd(II) cations in aqueous EtOH leads to M(L ^I,II -X, S) ₂ chelate complexes. The Cd(II) complex Cd(L ^I ) ₂ could not be isolated under analogous conditions because of its hydrolytic lability. The structure of the resulting compounds was studied by means of spectroscopy and microanalysis; in addition, the molecular structure of the complex Co(L ^II ) ₂ was elucidated by single crystal X-ray diffraction analysis. The cobalt atom is in a tetrahedral S₄ environment formed by the C=S and P=S sulfur atoms of two deprotonated ligands L ^II . The magnetic properties of Co(L ^I,II ) ₂ were investigated and the photoluminescent properties of the complexes are also reported.