Schiff base) were prepared. Photoacoustic (PA) spectroscopy was used to study physicochemical properties of the liquid crystalline metal complexes. In the region of ligand absorption, PA intensity increases for Eu(bta) 3 L 2 , La(bta) 3 L 2 , and Ho(bta) 3 L 2 , in that order. It is found that the PA intensity of the ligand bears a relation to the intramolecular energy transfer process. For the first time, phase transitions of Eu(bta) 3 L 2 from glass state to smectic A (SmA) phase and SmA phase to isotropic liquid are monitored by PA and fluorescence (FL) spectroscopy from two aspects: nonradiative and radiative transitions. The results show that PA technique may serve as a new tool for investigating the spectral properties and phase transitions of liquid crystals containing metal ions.