We describe a new methodology that sheds light on the fundamental electronic processes that occur at the subsurface regions of inorganic solid photocatalysts. Three distinct kinds of microscopic-, imaging are used that yield spatial, temporal, and energy-resolved information. We also carefully consider the effect of photon-induced near-field electron microscopy (PINEM), first reported by Zewail et al. in 2009. The value of this methodology is-illustrated by studying afresh a popular and viable photocatalyst, hematite, alpha-Fe2O3 that exhibits most of the properties required in a practical application. By employing high-energy electron-loss signals (of several hundred eV), coupled to femtosecond temporal resolution as well as ultrafast energy-filtered transmission electron microscopy in 4D, we have, inter alia, identified Fe4+ ions that have a lifetime of a few picoseconds, as well as associated photoinduced electronic transitions and charge transfer processes.