Narrow escape from confinement through a nanochannel is the critical step of complex transport processes including size-exclusion-based separations, oil and gas extraction from the microporous subsurface environment, and ribonucleic acid translocation through nuclear pore complex channels. While narrow escape has been studied using theoretical and computational methods, experimental quantification is rare because of the difficulty in confining a particle into a microscopic space through a nanoscale hole. Here, we studied narrow escape in the context of continuous nanoparticle diffusion within the liquid-filled void space of an ordered porous material. Specifically, we quantified the spatial dependence of nanoparticle motion and the sojourn times of individual particles in the interconnected confined cavities of a liquid-filled inverse opal film. We found that nanoparticle motion was inhibited near cavity walls and cavity escape was slower than predicted by existing theories and random-walk simulations. A combined computational-experimental analysis indicated that translocation through a nanochannel is barrier controlled rather than diffusion controlled.