The L 3 -edge x-ray absorption spectrum of Pa͑V͒ fluoride in aqueous solution show clear evidence for the double photoexcitation involving 2p and 4f electrons. A comparison with the ͓2p4f͔ double-electron excitations observed in the L 3 -edge x-ray absorption spectra of other actinides ͑thorium, uranium, neptunium, plutonium, and americium͒ indicates a monotonic increase in the excitation energy. The sharp edgelike structure of the multielectron excitation reveals the origin of a shake-up channel.