Laser-induced photoacoustic spectroscopy (LIPAS), which utilizes the photothermal effect that results from nonradiative relaxation of excited state molecules, was used in the speciation analysis of the complexes of neodymium(III) and water soluble synthetic polyelectrolyte, poly methacrylic acid (PMAA), in 0.1 M $NaClO_4$ at pH of 6.0. The minimum detection limit of Nd(III) by LIPAS was $5.O{ imes}10^{-6}$ M. Experiment was carried out at low concentration ratio of Nd(III) to PMAA to assure that 1 : 1 complexes predominate. The bound and free Nd(III) species were characterized by measuring nonradiative relaxation energy of the excited states $(^2GM{7/2};and;^4G_{5/2})$ to the metastable state $(^4G_{3/2})$. Two species were quantified by deconvolution of the mixed spectrum using their respective reference spectra. The conditional stability constant measured by LIPAS was 5.52 L$mol^{-1}$.