Time-dependent events during operation of SOFCs, i.e., performance enhancement and/or deterioration, can be readily observed for the cell composed of strontium-doped lanthanum manganite (LSM) cathode and yttria-stabilized zirconia (YSZ) electrolyte, concomitant with the change in interfacial structure of LSM/YSZ. The influence of LSM composition on the electrochemical properties and microstructure of LSM/YSZ interface during prolonged operation was investigated. Four different LSM cathodes were used and the change in microstructure, especially TPB-length, was evaluated quantitatively by a focused ion beam scanning electron microscope (FIB-SEM). For LSM cathodes with A-site deficient compositions, the change in TPB-length had a minor contribution to the performance enhancement after 20 h of galvanostatic operation. On the other hand, for 100 h duration an increase in cathode overpotential was confirmed, accompanied with the formation of thin layer of LSM over YSZ electrolyte. A series of phenomena were triggered by the change in oxygen nonstoichiometry of LSM under polarized states. The mechanism for microstructural change was proposed and the long-term stability of LSM/YSZ interface was discussed. (C) 2013 Elsevier B.V. All rights reserved.