Electron microscopy characterization across the cathode-electrolyte interface of two different types of intermediate temperature solid oxide fuel cells (IT-SOFC) is performed to understand the origin of the cell performance disparity. One IT-SOFC cell had a sprayed-cosintered Ce(0.90)Gd(0.01)O(1.95) (CGO10) barrier layer, the other had a barrier layer deposited by pulsed laser deposition (PLD) CGO10. Scanning electron microscopy, transmission electron microscopy (TEM), and electron backscattered diffraction (EBSD) investigations conclude that the major source of the cell performance difference is attributed to CGO-YSZ interdiffusion in the sprayed-cosintered barrier layer. From TEM and EBSD work, a dense CGO10 PLD layer is found to be deposited epitaxially on the 8YSZ electrolyte substrate-permitting a small amount of SrZrO(3) formation and minimizing CGO-YSZ interdiffusion.