The syntheses of the perchlorate salts of H(TEA)+ (1), Li(TEA)+ (2), Na(TEA)+ (3), Sr(TEA)2(2+) (4), and Ba(TEA)2(2+) (5), wherein TEA = triethanolamine, are reported. Characterizational NMR spectral results (H-1, C-13, Li-7, Na-23) as well as crystal structures for 1, 3, and 5 are discussed. The structures of 1, 3, and 5 reveal respectively the cation H(TEA)+ in which the proton is in a tetrahedral environment,a seven-coordinate sodium weakly coordinated by a monodentate ClO4- and two OH oxygens from neighboring units, and a [Ba(TEA)ClO4]2(2+) cation in which two weakly coordinating perchlorates bridge two Ba2+ ions in a bidentate fashion. Extensive hydrogen bridging via ClO4- ions occurs in all three compounds giving rise to parallel sheet structures. Crystal data : 1 (at 22-degrees-C), a = 9.086(1) angstrom and c = 23.919(6) angstrom, with Z = 6 in space group R3c; 3 (at 20-degrees-C), a = 9.617(1) angstrom, b = 7.787(1) angstrom, c = 15.914(2) angstrom, and beta = 105.80-degrees, with Z = 4 in space group P2(1)/c; 5 (at -50-degrees-C), a = 7.498(2) angstrom, b = 10.492(2) angstrom, c = 15.749(3) angstrom, alpha = 76.06(2)-degrees, beta = 80.56(2)-degrees, and gamma = 76.70(2)-degrees, with Z = 2 in space group P1BAR.