AbstractWarm dense matter is at the boundary between a plasma and a condensed phase and plays a role in astrophysics, planetary science and inertial confinement fusion research. However, its electronic structure and ionic structure upon irradiation with strong laser pulses remain poorly understood. Here, we use an intense and ultrafast X-ray free-electron laser pulse to simultaneously create and characterize warm dense copper using L-edge X-ray absorption spectroscopy over a large irradiation intensity range. Below a pulse intensity of 1015 W cm−2, an absorption peak below the L edge appears, originating from transient depletion of the 3d band. This peak shifts to lower energy with increasing intensity, indicating the movement of the 3d band upon strong X-ray excitation. At higher intensities, substantial ionization and collisions lead to the transition from reverse saturable absorption to saturable absorption of the X-ray free-electron laser pulse, two nonlinear effects that hold promise for X-ray pulse-shaping. We employ theoretical calculations that combine a model based on kinetic Boltzmann equations with finite-temperature real-space density-functional theory to interpret these observations. The results can be used to benchmark non-equilibrium models of electronic structure in warm dense matter.