This paper reports on the investigations of the chemical compatibility between SOFC cathode materials with compositions Pr(0.8)Sr(0.2)Co(0.2)Mn(0.8)O(3-delta), Pr(0.8)Sr(0.2)Co(0.2)Fe(0.8)O(3-delta), Pr(0.8)Sr(0.2)Co(0.3)Mn(0.7)O(3-delta) and Pr(0.75)Sr(0.2)Co(0.2)Mn(0.8)O(3-delta) and the electrolyte materials with compositions La(0.8)Sr(0.2)Ga(0.9)Mg(0.1)O(3-delta), and La(0.9)Sr(0.1)Ga(0.8)Mg(0.2)O(3-delta). The lanthanum gallate electrolyte with 20 mol.% Sr contained two additional phases, namely, LaSrGa(3)O(7) and LaSrGaO(4), while that with 10 mol.% Sr was formed in nearly single phase. Two types of experiments were performed: (a) reactivity experiments of powder mixtures and (b) diffusion experiments in cathode/electrolyte double-layer pellets. No reaction products were detected by XRD. High Co diffusion into the electrolyte was identified with SEM/EDX in all diffusion experiments examined. The transition metals diffuse in the order Mn < Fe < Co. La, Pr and Ga show a smaller tendency for diffusion. The diffusion of transition metal cations into the electrolyte La(0.8)Sr(0.2)Ga(0.9)Mg(0.1)O(3-delta) caused the destabilisation and disappearance of the second phases in the interdiffusion zone. In the case of the A-site deficient cathode, the formation of LaSrGa(3)O(7) second phase was identified on the electrolyte side, near the interdiffusion zone. (C) 2000 Elsevier Science B.V. All rights reserved.