The pseudo-tetrahedral complexes [CuL2]PF6 center dot 7H(2)O center dot CH3OH (1) and [AgL2]CF3SO3 center dot H2O (2) (L = 3,3'-bis(2-benzimidazolyl)-2,2'-bipyridine) have been synthesized and characterized through crystal structure analyses, electrochemistry, and spectroscopic methods. X-ray structural analyses of 1 and 2 indicate that sterically constrained N-4 ligands L are cis and behave as bidentate chelates to a single metal ion in a pseudo-tetrahedral fashion through the benzimidazole. As two benzimidazolyl rings exhibit considerable steric hindrance, the bipyridine unit of L remains uncoordinated. The pseudo-tetrahedral cation [CuL2](+) shows a quasi-reversible Cu-I/Cu-II oxidation-reduction wave in the CV in DMF (counter-ion PF6-). The fluorescence titration of L with copper(I), silver(I), and also with pH have been conducted to examine the selectivity. The ligand shows remarkably high selectivity and sensitivity for Ag(I).