The UV-Vis, NIR and MIR photoacoustic spectra of Pr(aa)3*2H2O were measured and most f-f transition peaks of Pr3+ are detected. The peak split and peak shift are studied also. The covalency parameter is calculated and it turns out that the covalent bonds between Pr(Ⅲ) ions and ligands exist. The results conclude that photoacoustic spectroscopy offers a unique and complementary method in analysis of solid rare earth complexes. Compared with conventional FT-IR transmission and absorption approaches, PAS has the advantages of fast, nondestructive analysis and high resolution.