Long-range electron transfer (ET) is a crucial step in many energy conversion processes and biological redox reactions in living organisms. We show that newly developed X-ray pulses can directly probe the evolving oxidation states and the electronic structure around selected atoms with detail not available through conventional time-resolved infrared or optical techniques. This is demonstrated in a simulation study of the stimulated X-ray Raman (SXRS) signals in Re-modified azurin, which serves as a benchmark system for photoinduced ET in proteins. Nonlinear SXRS signals offer a direct novel window into the long-range ET mechanism.