A range of compelling information on the local structure and dynamics of the ferroelectric perovskite-type (ABO 3 ) system (1−x)PbTiO 3 −xBiScO 3 has been revealed through analyzing room-temperature x-ray pair distribution functions and temperature-dependent Raman scattering data for compositions ranging across the morphotropic phase boundary (MPB). Raman scattering data have provided exclusive evidence for distinct dynamical responses from the A-site Pb/Bi and the B-site Ti/Sc cations as a function of composition and temperature. Both pair distribution function and Raman scattering analyses indicate improved coherence between the A-site and B-site off-center displacements for x above the MPB composition. The distinguishable dynamical features were spotted between two sets of compositional range from which x=0.34 could be assigned as a critical composition of “local” MPB: the composition at which the pathway of mesoscopic-scale temperature-driven coupling and transformation processes changes. This differs from the previous reports based on the analysis of the average structure, suggesting the response function of a system may not necessarily follow the evolution of the average structure from which however the MPB has so far been ascribed for a particular system. The individual features of the cations revealed here will further help in understanding the structure-property correlations for similar ferroelectric solid solutions.