The synthesis and characterization of naptho-9-crown-3, N9C3, as a novel 9-membered ring crown ether with greater lipophilicity than that of benzo-9-crown-3, B9C3, is reported. The solution AA'BB' pattern of -CH 2 O- protons in N9C3 is close to that of B9C3. The solid-phase 1 3 C CPMAS NMR, as a tool for conformation prediction, reveals that the solid-phase conformation of the 9-membered ring crown cavity in N9C3 is different from B9C3, the two key C2O2CH 2 and C3O1CH 2 units are predicted to be out of naphthalene plane, and the two C1C2O2CH 2 and C4C3O1CH 2 torsion angles are close to each other.