We present extensive investigations of the crystallographic phase diagram and electronic properties of the Fe-based superconductor FeSe under extreme conditions (high pressure (HP) and low temperature (LT)) by synchrotron X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). An isostructural phase transition (Tetragonal (T) →high-pressure Tetragonal (Tʹ)) is discovered in FeSe at ∼2.8 GPa based on the axial ratio c/a with finer pressure step as observed in Fe-As-based superconductor such as EuFe₂As₂. We also find a pressure-induced Tʹ → MnP-type phase transition at 7.6 GPa in FeSe, which is consistent with the documented pressure-induced high-spin → low-spin transition (∼6–7 GPa). These results reveal the pressure-induced structural phase transition sequence in FeSe at room temperature to be T → Tʹ → Tʹ+MnP-type at pressures of 0–10.6 GPa, enriching the crystallographic phase diagram. The HPLT XRD data also indicate that a sluggish structural phase transition (Cmma → Pnma) begins at 7.5 GPa, and these two phases coexist up to 26.5 GPa. The HP X-ray absorption near-edge spectroscopy (XANES) measurement shows that E_o of Se experiences a pressure-induced shift to high energy, evidencing strongly charge transfer between Fe and Se under high pressure. Our results shed lights on the correlation between crystallographic/electronic structure and superconductivity in this material.