The coordination chemistry of the macrobicyclic triscatecholate ligands bicappedTRENCAM (2), bicappedTPTTRENCAM (3), and bicappedTPTCAM (4), as well as the new ligand TPTCAM (5), has been investigated with Fe3+, V4+, Ti4+, and Ga3+. UV-visible spectroscopy suggests that the Fe(III) and the V(IV) compounds possess pseudooctahedral geometry at the central metal atom. The electrochemistry of the vanadium complexes of the above ligands and same comparison compounds ([V bicappedTRENCAM)](2-) (19), [V(ETA)](2-) (20)) has been probed by cyclic voltammetry. An exemplary 4d metal complex, [MoO2(H-2-bicappedTRENCAM)](2-) (24), has been prepared. As shown by the X-ray structure analysis of the dipotassium salt, this cis-MoO2 complex is formed by coordination of the cation external to the macrobicyclic ligand. Crystal data for MOK(2)C(36)H(38)N(8)O(14). DMF.5H(2)O : space group P2(1)/c (No. 14), a = 13.322(2) Angstrom, b = 14.252(2) Angstrom, c = 27.885(3) Angstrom, beta = 103.11(1)degrees, V = 5.157(3) Angstrom(3), and Z = 4.