New bifunctional H4dota-like ligands with three acetic acid and one phosphinic acid pendant arms and propionate (H5do3apPrA) or 4-aminobenzyl (H4do3apABn) reactive groups bound to the phosphorus atom were investigated. Potentiometric studies showed that the ligands have a similar basicity to the parent H4dota and the stability constants of their complexes with sodium(I) and selected lanthanide(III) ions are also similar. Formation and acid-assisted decomplexation kinetics of yttrium(III) complexes with a series of H4dota-like ligands (H4dota and its phosphinic/phosphonic acid analogues) were studied and the reactions are sensitive to a slight modification of the ligand structure. The (2-carboxyethyl)phosphinic acid derivative H5do3apPrA and the phosphonic acid ligand H5do3ap form complexes faster than H4dota. The most kinetically inert complex is that with H4do3apABn. Rates of complexation and decomplexation can depend on the ability to transfer proton(s) outside/inside the complex cavity.