The high-pressure behavior of jamesonite (FePb₄Sb₆S₁₄, a = 4.08(3) Å, b = 19.08(3) Å, c = 15.67(3) Å, β= 91.89°, space group P2₁/c) has been investigated using in situ HP synchrotron X-ray single-crystal diffraction up to ~17 GPa with a diamond anvil cell under hydrostatic conditions. Results of the volume isothermal equation of state (EoS), determined by fitting the P-V data with a third-order Birch–Murnaghan (BM) EoS, are V₀ = 1207.1(4) ų, K₀ = 36(1) GPa and K’ = 5.7(7). At high pressure, jamesonite undergoes a phase transition to an orthorhombic structure with a Pmcb space group (β-jamesonite). The analysis of β-jamesonite’s compressibility up to 16.6 GPa, studied by fitting the data with a second-order BM-EoS, gives V₀ = 1027(2) ų, K₀ = 74(2) GPa. The comparison of the structural refinements at different pressures indicates that Fe, Pb and Sb do not change their coordination number over the whole investigated P range, respectively, 6 for Fe, 7 and 8 for Pb and 5 + 2 for Sb. However, a significant change occurs on the orientation of Sb lone electron pairs upon the phase transition in accordance with the change in symmetry. Furthermore, a discontinuity in the Fe chain evolution at the transition pressure is observed.