Cerium phosphide undergoes a unit-cell volume discontinuity without any structural phase transitions upon application of a high pressure of ∼10 GPa. This phenomenon is attributed to a change in the electronic charge distribution of the cerium in CeP, but to date no direct experimental verification for this hypothesis has been presented. Here, we report a Ce L3-edge X-ray absorption spectroscopy study under pressure, which provides direct compelling evidence of an electronic transition associated with the above-mentioned isostructural volume discontinuity. The present results should be relevant to the understanding of the phenomenon of pressure induced isostructural transitions involving unit-cell volume collapse.