The coordination chemistry of the imidazolidinylpyridine ligand with Ni(II), Cu(II), Cd(II), and Zn(II) ions was investigated in both protic and aprotic solvents. Interestingly, the coordination environment around the metal center varied significantly depending upon the nature of metal ion and solvent used for synthesis. In acetonitrile the imidazolidinylpyridine bound to Cu(II) and Ni(II) remains intact, while in methanol it formed ring-opened hemiaminal ether. The Cd(II) and Zn(II) ion stabilized the imidazolidinylpyridine as a face-capping tridentate ligand regardless of the nature of the solvent. The imidazolidinylpyridine and the complexes formed were characterized by NMR spectroscopy, high resolution electrospray ionization mass spectrometry and single-crystal X-ray crystallography, appropriately. The structural features in the solid-state structures were particularly intriguing, shedding light on the complex interplay between the ligand, metal ions, and solvent environments in coordination chemistry.