Pb(Fe0.5-xScxNb0.5)O3 [(PFSN) (0 ≤ x ≤ 0.5)] multiferroic relaxors were synthesized and the temperature dependence of phonon modes across ferroelectric to paraelectric transition was studied. With varying Sc content from x = 0 to 0.25 the structure remains monoclinic and with further addition (x = 0.3 - 0.5) the structure transforms into rhombohedral symmetry. Structural refinement studies showed that the change in crystal structure from monoclinic to rhombohedral symmetry involves a volume increment of 34-36%. Associated changes in the tolerance factor (1.024 ≤ t ≤ 0.976) and bond angles were observed. Structure assisted B′-B″ cation ordering was confirmed through the superlattice reflections in selected area electron diffraction (SAED) pattern of Pb(Sc0.5Nb0.5)O3 (x = 0.5). Cation ordering is also evident from the evolution of Pb-O phonon mode in Raman spectra of compositions with rhombohedral symmetry (x ≥ 0.3). The high temperature Raman scattering studies show that the B-localized mode [F1u, ∼250 cm-1] and BO6 octahedral rotational mode [F1g, ∼200 cm-1], both originating from polar nano regions (PNRs) behave like coupled phonon modes in rhombohedral symmetry. However, in monoclinic symmetry they behave independently across the transition. Softening of B localized mode across the transition followed by the hardening for all compositions confirms the diffusive nature of the ferroelectric transformation. The presence of correlation between the B localized and BO6 rotational modes introduces a weak relaxor feature for systems with rhombohedral symmetry in PFSN ceramics, which was confirmed from the macroscopic dielectric studies. © 2016 Author(s).