A synthetic protocol has been designed to incorporate the DO3A ligand to the focal point of cationic or anionic carbosilane dendrons, affording a set of bifunctional chelating agents (BFCAs) useful for potential biomedical applications. The complexation behavior study of ionic BFCAs has been accomplished by UV-vis and electron paramagnetic resonance spectroscopy as well as potentiometric titrations. The presence of the dendron branches modifies the complexation capacity of the macrocyclic ring with respect to that of the 1,4,7,10-tetraazacyclodocecane-N,N',N″,N‴-tetraacetic acid (DOTA) ligand. Also, a different behavior has been observed in the carboxylate-terminated dendrons against analogous sulfonate- or amine-terminated dendrons in the contribution of the branches and peripheral groups to the coordination modes. The presence or not of Cu-S2O2 coordination sites and the generation can be important factors to take into account for considering a particular biomedical application.