We experimentally investigate diffraction of a Rb-87 Bose-Einstein condensate from a one-dimensional optical lattice. We use a range of lattice periods and timescales, including those beyond the Raman-Nath limit. We compare the results to numerical solutions of the Gross-Pitaevskii equation and classical calculations, with quantitative and qualitative agreement, respectively. The classical calculations predict that the envelope of the time-evolving diffraction pattern is shaped by caustics: singularities in the phase-space density of classical trajectories. This behavior becomes increasingly clear as the lattice period grows.