Four C-3-functionalized cyclotriveratrylene (CTV) derivatives 1-4 were synthesized, and the ion selectivity of CTV derivatives for inorganic ions was evaluated. Upon potentiometric measurements, CTV derivatives bearing three quinolinylmethyl or pyridinylmethyl groups (1 or 2) were found to exhibit high selectivity for the Ag+ ion. However, CTV derivatives bearing three benzyl or cyclohexylmethyl groups (3 or 4) exhibited rather high selectivity for the Li+ ion. The aromatic nitrogen and methoxy oxygen atoms in the CTV derivatives were observed to play important roles as effective coordination donor sites for the Ag+ or the Li+ ions.