Single crystals 0.26BiScO3-0.25Pb(Mg1/3Nb2/3)O3-0.49PbTiO3 [BSPMNT] have been grown for the first time by the solid-state crystal growth (SSCG) method. A <110> oriented Ba(Zr,Ti)O3 crystal seed was embedded in a matrix of BSPMNT compact which was annealed at high temperatures to induce the single crystal growth. Various fluxes, including Bi2O3, LiBiO2, PbO/LiBiO2, and PbO/Bi2O3, were used and their effects on the microstructure of the annealed compacts and the single crystal growth behavior were investigated. In the annealed samples with PbO/Bi2O3 flux, a considerable single crystal growth occurred at 1050 °C (with thickness on the order of 500–1000 μm), without the formation of abnormally large grains in the matrix. The results were explained in terms of the effect of various fluxes, based on the grain growth theory.