An understanding of potassium chemistry in energy conversion processes supports the development of complex biomass utilization with high efficiency and low pollutant emissions. Potassium exists mainly as potassium hydroxide (KOH), potassium chloride (KCl), and atomic potassium (K) in combustion and related thermochemical processes. We report, for the first time, the measurement of the ultraviolet (UV) absorption cross sections of KOH and KCl at temperatures between 1300 K and 1800 K, using a newly developed method. Using the spectrally resolved UV absorption cross sections, the concentrations of KOH and KCl were measured simultaneously. In addition, we measured the concentrations of atomic K using tunable diode laser absorption spectroscopy, both at 404.4 and 769.9 nm. The 404.4 nm line was utilized to expand the measurement dynamic range to higher concentrations. A constant amount of KCl was seeded into premixed CH4/air flames with equivalence ratios varied from 0.67 to 1.32, and the concentrations of KOH, KCl, and atomic K in the hot flue gas were measured nonintrusively. The results indicate that these techniques can provide comprehensive data for quantitative understanding of the potassium chemistry in biomass combustion/gasification.