We report pressure-induced structural changes in PbSc(0.5)Ta(0.5)O3 studied by single-crystal x-ray diffraction and Raman scattering. The appearance of a soft mode, a change in the volume compressibility, broadening of the diffraction peaks, and suppression of the x-ray diffuse scattering show that a phase transition occurs near pc approximately 1.9 GPa. The critical pressure is associated with a decoupling of the displacements of the B site and Pb cations in the existing polar nanoregions, leading to the suppression of B-cation off-center shifts and enhancement of the ferroic distortion in the Pb-O system.