The stability constants and structure of the complexes of CdII and ZnII with 1-ethoxymethylimidazole (ExMeIm), 1-propoxymethylimidazole (PxMeIm), 1-ethoxymethyl-2-methylimidazole (ExMe-2-MeIm) and 1-propoxymethyl-2-methylimidazole (PxMe-2-MeIm) in aqueous solution have been determined by potentiometric methods. ZnII form both tetrahedral and octahedral species with the cited ligands according to the configurational equilibrium type: octahedron ↔ tetrahedron, but CdII prefers octahedral coordination of alkoxymethylimidazole complexes in aqueous solution. Retention of the six-coordination form of CdII has also been confirmed by the data obtained for two novel compounds which have been synthesized in the solid state. The crystal and molecular structure of [Cd(ExMeIm)4(NO3)2] (1) has been determined by X-ray diffraction. The coordination geometry around the CdII ion can be considered as slightly distorted tetragonal bipyramidal (CdN4O2). Additionally, another six-coordinate CdII compound with ethoxymethyl-2-methylimidazole [Cd(ExMe-2-MeIm)4(H2O)](NO3)2 (2) has been characterized by spectroscopic (i.r., far i.r., Raman) ES–MS and t.g.a. methods.