The present study was dedicated to the classical piezoelectric, lead-zirconate-titanate ceramic with composition Pb(Zr 0.54Ti 0.46)O 3 at the Zr-rich side of the morphotropic phase boundary at which two phases co-exists. The pressure-induced changes in the phase fractions were studied by high-pressure neutron powder diffraction technique up to 3 GPa and 773 K. The two co-existing phases were rhombohedral R 3 c and monoclinic C m at room temperature and R 3 c and P 4 m m above 1 GPa and 400 K. The experiments show that pressure favors the R 3 c phase over the C m and P 4 m m phases, whereas at elevated temperatures entropy favours the P 4 m m phase. At 1 GPa pressure, the transition to the cubic P m 3 m phase occurred at around 600 K. Pressure lowers the C m → P 4 m m transition temperature. The C m phase was found to continuously transform to the P 4 m m phase with increasing pressure, which is inline with the usual notion that the hydrostatic pressure favours higher symmetry structures. At the same time, the phase fraction of the R 3 c phase was increasing, implying discontinuous C m → R 3 c phase transition. This is in clear contrast to the polarization rotation model according to which the C m would link the tetragonal and rhombohedral phases by being a phase in which the polarization would, more or less continuously, rotate from the tetragonal polarization direction to the rhombohedral direction. Pressure induces large changes in phase fractions contributing to the extrinsic piezoelectricity. The changes are not entirely reversible, as was revealed by noting that after high-pressure experiments the amount of rhombohedral phase was larger than initially, suggesting that on the Zr-rich side of the phase boundary the monoclinic phase is metastable. An important contribution to the intrinsic piezoelectricity was revealed: a large displacement of the B cations (Zr and Ti) with respect to the oxygen anions is induced by pressure.