Quantum-mechanical transitions arising under optical excitation of globular photonic crystals are analyzed. Possible cases of electron—phonon and electron—photon—phonon coupling initiated by laser pumping are discussed. Spectral characteristics of acoustic waves emitted during electron—phonon transitions in synthetic opal are calculated. The maximum frequency of arising electromagnetic radiation is estimated. The crucial role of free electrons localized within globules in excitation of radiative processes in the crystal is accented.