The structural stability of γ-boron is investigated using Raman spectra and DFT calculations under high pressures, up to 126 GPa, at ambient temperature. The pressure dependence of all the Raman-active modes of the γ-boron is reported. We also observe amusing changes within the B3g and B1g Raman-active vibrational modes, which result in the phenomenon of first merging and then separating the Raman peaks. In addition to the Raman measurements, the changes in crystal structure and force constants are calculated to reasonably explain the discrepancy between the two Raman modes in response to pressure. The results of the continuous shifts for all Raman modes and the unit-cell parameters, as well as volume with increasing pressure, indicate that there is no structural transformation of γ-boron below this pressure value, with no changes in either symmetry or structure.