Rydberg excitons are, with their ultrastrong mutual interactions, giant optical nonlinearities, and very high sensitivity to external fields, promising for applications in quantum sensing and nonlinear optics at the singlephoton level. To design quantum applications it is necessary to know how Rydberg excitons and other excited states relax to lower-lying exciton states. Here, we present photoluminescence excitation spectroscopy as a method to probe transition probabilities from various excitonic states in cuprous oxide. We show giant Rydberg excitons at T = 38 mK with principal quantum numbers up to n = 30, corresponding to a calculated diameter of 3 mu m.