(Ba0.5Sr0.5)(Co0.8Fe0.2)O3-delta (BSCF) with mixed ionic and electronic conductivity is promising as oxygen separation membrane. However, its exceptional oxygen permeability is linked to the cubic perovskite phase, which destabilizes below 825 degrees C. This work is concerned with the stabilizing effect of partial B-site substitution in BSCF by Ti (10%) and Nb (5% and 10%). In addition, the effect of B-site substoichiometry on the formation of CoO precipitates as nucleation sites for other secondary phases is studied. The focus of this work is laid on the analysis of the phase constitution in bulk material between 600 and 800 degrees C. Scanning electron microscopy and (scanning) transmission electron microscopy with high spatial resolution in combination with energy-dispersive X-ray spectroscopy are applied which allow to detect even small volume fractions of secondary phases. It is confirmed by quantitative analysis that Ti and Nb substitution reduces the formation of secondary phases up to similar to 95%. There is a solubility limit of Nb in BSCF, which leads to the precipitation of Nb-rich precipitates already at 5% Nb substitution in contrast to Ti which is fully soluble even at 10% substitution. Despite of that, BSCF doped with 5% Nb in combination with 5% substoichiometric B-site occupation is the most promising material, because it shows the lowest overall volume fraction of secondary phases (similar to 0.8 vol% at 700 degrees C) and an almost negligible degradation rate in additionally recorded long-term resistivity measurements.