As a promising environment-friendly alternative to current vapor-compression refrigeration, solid-state refrigeration based on the barocaloric effect has been attracting worldwide attention. Generally, both phases in which a barocaloric effect occurs are present at ambient pressure. Here, instead, we demonstrate that KPF6 exhibits a colossal barocaloric effect due to the creation of a high-pressure rhombohedral phase. The phase diagram is constructed based on pressure-dependent calorimetric, Raman scattering, and neutron diffraction measurements. The present study is expected to provide an alternative routine to colossal barocaloric effects through the creation of a high-pressure phase.