Unusual phase transitions driven by electron correlation effects occur in many f-electron metals (lanthanides and actinides alike) from localized phases to itinerant phases at high pressures. The dramatic changes in atomic volumes and crystal structures associated with some of these transitions signify equally important changes in the underlying electronic structure of these correlated f-electron metals. Yet, the relationships among the crystal structure, electronic correlation and electronic structure in f-electron metals have not been well understood. In this study, utilizing recent advances in third-generation synchrotron x-ray spectroscopies and high-pressure diamond-anvil cell technologies, we describe the pressure-induced spectral changes across the volume collapse transition in Gd at 60 GPa and well above. The spectral results suggest that the f-electrons of high-pressure Gd phases are highly correlated even at 100 GPa – consistent with the Kondo volume collapse model and the recent experimental evidence of strong electron correlation of α-Ce.