To pursue the design of in vivo stable chelating systems for radiometals, a concise and straightforward method toolbox was developed combining NMR, isothermal titration calorimetry (ITC), and europium time-resolved laser-induced fluorescence spectroscopy (Eu-TRLFS). For this purpose, the macropa chelator was chosen, and Lu³⁺, La³⁺, Pb²⁺, Ra²⁺, and Ba²⁺ were chosen as radiopharmaceutically relevant metal ions. They differ in charge (2+ and 3+) and coordination properties (main group vs lanthanides). ¹H NMR was used to determine four pK_a values (±0.15; carboxylate functions, 2.40 and 3.13; amino functions, 6.80 and 7.73). Eu-TRLFS was used to validate the exclusive existence of the 1:1 Mⁿ⁺/ligand complex in the chosen pH range at tracer level concentrations. ITC measurements were accomplished to determine the resulting stability constants of the desired complexes, with log K values ranging from 18.5 for the Pb-mcp complex to 7.3 for the Lu-mcp complex. Density-functional-theory-calculated structures nicely mirror the complexes’ order of stabilities by bonding features. Radiolabeling with macropa using ligand concentrations from 10^-3 to 10^-6 M was accomplished by pointing out the complex formation and stability (²¹²Pb > ¹³³La > ¹³¹Ba ≈ ²²⁴Ra > ¹⁷⁷Lu) by means of normal-phase thin-layer chromatography analyses.