The high-pressure behaviour of two representative palmierite-type Pb3(PxAs1–xO4)2 ferroelastic compounds with x = 0 and 0.80 was analyzed by combined single-crystal X-ray diffraction and Raman spectroscopy. Single-crystal diffraction measurements on the As-rich compound Pb3(P0.20As0.80O4)2 show that it undergoes the same macroscopic monoclinic to trigonal phase transition as previously observed in pure Pb3(PO4)2 but with a significantly lower transition pressure, pc = 0.90(4) GPa for x = 0.80 as opposed to pc = 1.81(1) for x = 0.0. Synchrotron X-ray diffraction experiments reveal that both compounds exhibit significant diffuse scattering in a pressure interval of ~1.5 GPa above the corresponding pressure-induced transitions, indicating the persistence of monoclinic nanodomains within the macroscopically trigonal phase above the phase-transition point, similar to the high-temperature structural state. Raman spectroscopy reveal quite distinct lattice dynamics for x = 0 and x = 0.80, indicating different pathways of pressure-driven structural alteration. The pure phosphate compound shows a displacive phase transition of thermodynamically second-order type, whereas the As-rich compound exhibits an order-disorder phase transition with multistep structural changes on the mesoscopic scale. The pressure evolution of the Pb phonon modes as well as the broadening of the X-ray diffraction peaks suggests a further pressure-induced phase transition occurring in the range 5–7 GPa for Pb3(P0.20As0.80O4)2, whilst no indication for a second phase transition up to 10 GPa was observed for Pb3(PO4)2.