Spatially resolved analyses, by energy-dispersive X-ray spectroscopy ͑EDS͒ and scanning electron microscopy, allowed the quantification of exogenous Si contamination in a solid oxide fuel cell ͑SOFC͒ cathode after operation. The Si quantification, taking into account the endogenous Si impurity level, correlated well with the expectation from the condensation of Si͑OH͒ 4 vapor, originating from upstream alloy components and saturated in the hot inlet air. At higher resolution, EDS-transmission electron microscopy pointed out the deposition of Si vapor in the form of amorphous SiO 2 , blocking oxygen incorporation into the electrolyte phase within a composite SOFC cathode.In solid oxide fuel cell ͑SOFC͒ technology, silicon ͑Si͒ is, by its insulating and glass-forming properties, a major limitation for electrochemical performance. 1,2 As endogenous impurity in SOFC ceramics, Si is present in raw materials and is introduced by costcutting exercises during powder preparation. 3 Besides bulk impurity, exogenous Si contamination is vehicled in SOFC operation by the reactants, stemming from oils and greases as well as mineral dust. 2,4-6 In particular, cell-proximal system components such as furnace materials 7-9 or the common use of quartz reactors can lead to Si contamination. [10][11][12] Although the presence of Si is ubiquitous and influences both the electrolyte and cathode resistivities, 13 the understanding of its effect on electrochemical cathode processes, by a deleterious poisoning of the active catalytic sites for oxygen reduction, is lacking. 14 Moreover, it is suggested that different Si contamination levels are at least partially responsible for disagreements in the literature related to cathode performance and degradation, 13 as well as for the laboratory specific behavior of SOFC electrodes. 2,15 To enable data correlation from different researches, quantification methods for Si contamination are needed; 16 an area where this study aims to contribute. Energy-dispersive X-ray spectroscopy ͑EDS͒ is employed here as an identification and quantification tool for both endogenous Si impurity levels and Si contamination stemming from exogenous sources.