Phase pure Pb[(Fe0.5-xScx)Nb0.5]O3 [x = 0 to 0.5] multiferroic relaxors have been synthesized to study the effect of Sc on dielectric phase tansition. Rietveld refinement of x-ray diffraction patterns confirm that the structure transforms from monoclinic (Cm) to rhomobohedral (R3m) at x = 0.3. Absence of low frequency dielectric response in compositions with low Sc content attributed to interfacial polarizabilty arising due to differences in conductivities of grain and grain boundary. Moreover, value of diffusivity parameter (γ) of high of Sc content compositions is near to 2, confirms relaxor charactertistic of these compositions. However, an essential feature of relaxors i.e., frequency dependent dielectric permittivity as a function of temperature is observed only in x = 0.5 composition [Pb(Sc0.5Nb0.5)O3 (PSN)]. In addition, ferroelectric phase transition temperature (Tmax) increases initially at lower Sc content (upto x ≤ 0.25), and further drops beyond x ≥ 0.3. Such behavior of Tmax in these compositions is due to the onset of B'-Blocal cation ordering at x = 0.3. High temperature Raman spectra of Pb(Sc0.5Nb0.5)O3 (x = 0.5) confirm the stability of cation ordering in compositions with high Sc content well above the phase transition temperature. © 2016 Materials Research Society.