BiFeO3 and PbTiO3 were introduced to a Sc-modified Pb(Fe2/3W1/3)O3 compound with strong cation order to improve the multiferroic properties. It is found that the degree of cation order decreases as the amount of BiFeO3 or PbTiO3 increases. As a result, the saturation magnetization deteriorates. Solid solutions with BiFeO3 show an increase in both ferroelectric and magnetic transition temperatures. However, the ferroelectric remanent polarization is dramatically suppressed. In contrast, solid solution with PbTiO3 leads to an increase in the ferroelectric transition temperature, a decrease in the magnetic transition temperature, and a significant enhancement of remanent polarization. The composition 0.93[0.79Pb(Fe2/3W1/3)O3–0.21Pb(Sc2/3W1/3)O3]–0.07PbTiO3 shows the optimized properties of Tmax of 208K, Pr of 3.6μC/cm2 between 120 and 210K, TN of 209K, and Ms of 0.23μB/f.u. (3.7emu/g) at 10K under 5T.