The primary crystallization field of a perovskite solid solution Bi1-xSrxMnO3-delta was delimited by calculating the respective phase equilibria in the quaternary Bi-Sr-Mn-O system. The calculations are based on the recent assessment involving all three ternary subsystems, a quaternary liquid approximated as a mixture of Mn, MnO, Mn2O3, SrO and Bi2O3 species with binary Redlich-Kister coefficients and the perovskite phase described in terms of a point defect model allowing Sr2+ for Bi3+ substitution, oxygen vacancy formation and the related Mn3+/Mn4+ mixing on Mn-sublattice. The crystallization path and the composition of the crystallized solid solution are compared with single crystal growth experiments performed by self-flux method from a Bi-rich melt. The crystallization path obtained for a selected feed composition for which the largest and high quality single crystal have been grown, turns out to end very close to the global eutectic point. (c) 2006 Elsevier B.V. All rights reserved.