© 2018 American Physical Society. Understanding electron-electron correlations in matter ranging from atoms to solids represents a grand challenge for both experiment and theory. These correlations occur on attosecond timescales and have only recently become experimentally accessible. In the case of highly excited systems, the task of understanding and probing correlated interactions is even greater. In this work, we combine state-of-the-art light sources and advanced detection techniques with ab initio calculations to unravel the role of electron-electron correlation in D2 photoionization by mapping the dissociation of a highly excited D2+ molecule. Correlations between the two electrons dictate the pathways along which the molecule dissociates and lead to a superposition of excited ionic states. Using 3D Coulomb explosion imaging and electron-ion coincidence techniques, we assess the relative contribution of competing parent ion states to the dissociation process for different orientations of the molecule with respect to the laser polarization, which is consistent with a shake-up ionization process. As a step toward observing coherent superposition experimentally, we map the relevant nuclear potentials using Coulomb explosion imaging and show theoretically that such an experiment could confirm this coherence via two-path interference.