In this Letter, we report on the experimental characterization of the geometry of short-lived electronically excited states in organic solids by time-resolved x-ray diffraction. Here, the structure factor of the organic crystal is measured as a function of time. Since this technique gives complete structural information, it is a very useful tool for learning more about atom motions on the excited-state energy surface-"beyond" the broad band typical of conventional spectroscopy. Although we used molecular crystals rather than free molecules, the compounds show detectable transient structural changes on the ps to ns time scale in our study.