In the frame of a systematic study on the sequestering ability of natural antioxidants towards metal cations, here the complexation of coumarin-3-carboxilic acid (HCCA) with Pb(II) and the overall stability constants of the resulting complexes, at 37 °C and in 0.16 M NaClO4, are discussed. Reaction of Pb(ClO4)2 with HCCA in an aqueous medium at a pH range from 2 to 6 and various ratios (1:1–1:10) yielded the Pb–CCA complexes, which were characterized spectrometrically by laser desorption ionization mass spectrometry (LD-MS). LD-MS has provided the composition and structure of Pb–CCA species according to the speciation model proposed on the basis of the potentiometric data. The graphic representation of the complex’s concentration curves is given by the distribution diagram, which provides a whole depiction of the species present in the solution at the selected pH ranges.