The high-pressure metallization and electrical transport behaviors of GaSb were systematically investigated using in situ temperature-dependent electrical resistivity measurements, Hall effect measurements, transmission electron microscopy analysis, and first-principles calculations. The temperature-dependent resistivity measurements revealed pressure-induced metallization of GaSb at approximately 7.0 GPa, which corresponds to a structural phase transition from F-43m to Imma. In addition, the activation energies for the conductivity and Hall effect measurements indicated that GaSb undergoes a carrier-type inversion (p-type to n-type) at approximately 4.5 GPa before metallization. The first-principles calculations also revealed that GaSb undergoes a phase transition from F-43m to Imma at 7.0 GPa and explained the carrier-type inversion at approximately 4.5 GPa. Finally, transmission electron microscopy analysis revealed the effect of the interface on the electrical transport behavior of a small-resistance GaSb sample and explained the discontinuous change of resistivity after metallization. Under high pressure, GaSb undergoes grain refinement, the number of interfaces increases, and carrier transport becomes more difficult, increasing the electrical resistivity.