AbstractUltrafast laser pump-probe methods allow chemical reactions to be followed in real time, and have provided unprecedented insight into fundamental aspects of chemical reactivity. While evolution of the electronic structure of the system under study is evident from changes in the observed spectral signatures, information on rearrangement of the nuclear framework is generally obtained indirectly. Disentangling contributions to the signal arising from competing photochemical pathways can also be challenging. Here we introduce the new technique of three-dimensional covariance-map Coulomb explosion imaging, which has the potential to provide complete three-dimensional information on molecular structure and dynamics as they evolve in real time during a gas-phase chemical reaction. We present first proof-of-concept data from recent measurements on CF₃I. Our approach allows the contributions from competing fragmentation pathways to be isolated and characterised unambiguously, and is a promising route to enabling the recording of ‘molecular movies’ for a wide variety of gas-phase chemical processes.