Short-lived core-ionized neon atoms were investigated by measuring under resonant Raman conditions the Auger decay following the excitation of a second core electron into a Rydberg state. Making use of intense and narrow bandwidth x-ray free-electron laser pulses, the photoexcitation spectrum of the femtosecond-lived Ne series was characterized. Energy position and lifetimes of the lower-lying Rydberg states were determined and the final state configurations following the decay of the Ne double-core hole resonance were partially resolved.