Resonance Raman spectroscopy as a probe of the early stages in the dissociation dynamics of polyatomic molecules has become a valuable complement to photofragmentation studies. While these spontaneous Raman experiments are obtained in the frequency domain, they often reflect evolution of the molecule during the first few femtoseconds of bond breaking. Coupled with progress in classical and quantum calculations of large-amplitude motion, unique insights have become available for a number of small polyatomic molecules. The development of this field to date is reviewed.