The thiourea derivative N,N-diethyl-N′-2-naphthoylthiourea (1) and three N-(dialkylaminothiocarbonyl)-N′-(1-naphthyl)-arylamidines (2-4) have been synthesized and CuII-, NiII- and PdII-complexes of them have been prepared. According to the X-ray structure analyses 1 with CuII and NiII under deprotonation forms neutral bis-chelates of nearly square-planar coordination with a cis arrangement of the O and S ligator atoms. Using their N and S atoms in 1,3 position as ligators, 2-4 in deprotonated form coordinate to CuII and PdII as neutral bis-chelates, in the case of CuII with a distorted tetrahedral coordination. PdII is coordinated square planar and has, probably due to the spatial influence of the 1-naphthyl groups, a trans arrangement of the N and S ligator atoms.