The photoacoustic(PA) studies of the nonradiative processes in dibenzoylmethide(DBM) Sm3+complex:Sm(DBM)3are reported. Compared with the PA spectra of La(DBM)3and Gd(DBM)3, the paramagnetic effect of the 4f-electrons of Sm3+to DBM and the intramolecular energy transfer from DBM to Sm3+is discussed. The excitation spectra of Sm(DBM)3are also reported to study the relaxation properties of Sm3+and the energy transfer between DBM and Sm3+. A model of relaxation and energy transfer processes of Sm(DBM)3is established.