Coordination complexes of some divalent metal ions with the DTPA (diethylenetriaminepentaacetic acid)based chelating surfactant 2-dodecyldiethylenetriaminepenta-acetic acid (4-C-12-DTPA) have been examined in terms of chelation and solution behavior. The headgroup of 4-C-12-DTPA contains eight donor atoms that can participate in the coordination of a metal ion. Conditional stability constants for five transition metal complexes with 4-C-12-DTPA were determined by competition measurements between 4-C-12-DTPA and DTPA, using electrospray ionization mass spectrometry (ESI-MS). Small differences in the relative strength between the coordination complexes of DTPA and 4-C-12-DTPA indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. The coordination of Cu2+ ions was investigated in particular, using UV-visible spectroscopy. By constructing Job's plots, it was found that 4-C-12-DTPA could coordinate up to two Cu2+ ions. Surface tension measurements and NMR diffusometry showed that the coordination of metal ions affected the solution behavior of 4-C-12-DTPA, but there were no specific trends between the studied divalent metal complexes. Generally, the effects of the metal ion coordination could be linked to the neutralization of the headgroup charge of 4-C-12-DTPA, and the resulting reduced electrostatic repulsions between adjacent surfactants in micelles and monolayers. The pH vs concentration plots, on the other hand, showed a distinct difference between 4-C-12-DTPA complexes of the alkaline earth metals and the transition metals. This was explained by the difference in coordination between the two groups of metal ions, as predicted by the hard and soft acid and base (HSAB) theory.