Lanthanide complexes of two tris(amide) derivatives of PCTA were synthesized and characterized. The relaxometric and luminescence properties of their lanthanide complexes were investigated as bimodal magnetic resonance (MR) and optical imaging agents. Luminescence studies show that one of the Tb(III) complexes dimerizes in solution at low millimolar concentrations, whereas the other may have a higher than expected coordination number in solution. The corresponding Gd(III) complexes display unusually high T(1) relaxivities and enhanced kinetic inertness compared to GdPCTA. These features suggest that these new chelates may be suitable for in vivo applications. The fast water-exchange rates observed for these complexes make them unsuitable as paramagnetic chemical exchange saturation transfer (PARACEST) agents.