The phase equilibria in the ½Nd 2 O 3 -BaO-½Fe 2 O 3 system were systematically studied at 1373 K in air and presented in the form of a phase diagram. By X-ray diffraction (XRD) analysis of quenched samples, the homogeneity ranges and crystal structure were determined for the following intermediate oxides: Nd 1-x Ba x FeO 3-δ with 0.0 ≤ x ≤ 0.05 (space group (SG) Pnma) and with 0.6 ≤ x ≤ 0.7 (SG Pm-3m), Ba 6+y Nd 2-y Fe 4 O 15-δ with 0.0 ≤ y ≤ 0.4 (SG P6 3 mc), and Ba 1.1 Nd 1.9 Fe 2 O 7-δ (SG P4 2 /mnm). The structural parameters of single-phase oxides were refined by the Rietveld method. The changes in oxygen content for Nd 1-x Ba x FeO 3-δ (0.6 ≤ x ≤ 0.7), Ba 6 Nd 2 Fe 4 O 15-δ , and Ba 1.1 Nd 1.9 Fe 2 O 7-δ versus temperature in air were determined by thermogravimetric analysis. Gradual substitution of neodymium by barium in the Nd 1-x Ba x FeO 3-δ (0.6 ≤ x ≤ 0.7) oxides leads to a decrease of oxygen content. Partial ordering via formation of separate domains with a p × a p × 5a p superstructure in Nd 0.4 Ba 0.6 FeO 3-δ , which cannot be detected by XRD, noticeably influence its thermal expansion and electrical conductivity.