Light and lattice vibrations in a crystal do not interact strongly in general, but both interact strongly with electrons. This three-way interaction allows a characterization method known as double resonance Raman spectroscopy to map out the low-energy electronic structure of materials and assign vibrational signatures to different microscopic processes. Double resonance in two-dimensional MoS2 reveals the dynamics of excitons – robust elementary excitations of a 2D crystal – between two sets of low-energy states known as valleys. The accurate assignment of vibrational signatures elucidates the essential physics limiting the performance of a novel class of “valleytronic” devices exploiting the selectivity of valleys to incident light carrying different polarizations.