XANES K-edge spectra of potassium promoter in precipitated Fe catalysts were acquired following activation by carburization in CO and as a function of time on-stream during the course of a Fischer-Tropsch synthesis run for a 100Fe:2K catalyst by withdrawing catalysts, sealed in wax product, for analysis. CO-activated and end-of-run spectra of the catalyst were also obtained for a 100Fe:5K catalyst. Peaks representing electronic transitions and multiple scattering were observed and resembled reference spectra for potassium carbonate or potassium formate. The shift in the multiple scattering peak to higher energy was consistent with sintering of potassium promoter during the course of the reaction test. The catalyst, however, retained its carbidic state, as demonstrated by XANES and EXAFS spectra at the iron K-edge, suggesting that sintering of potassium did not adversely affect the carburization rate, which is important for preventing iron carbides from oxidizing. The method serves a starting point for developing better understanding of the chemical state and changes in structure occurring with alkali promoter.