A new method for real-time measurements of potassium and sodium containing aerosol particles is described and verified. The method is based on surface ionization technique and may be used to explore the alkali chemistry related to high temperature chemistry processes. The measurement device is a further development of the simple and cost-effective surface ionization detector previously used for online alkali measurements in combustion and gasification research. The discrimination between sodium and potassium is possible due to differences in their surface desorption kinetics and facilitated by rapidly reversing the field potential between the ion source and the nearby collector. The instrument is evaluated in a series of laboratory experiments using size-selected alkali salt particles containing KCl, NaCl, K2SO4, Na2SO4, KNO3 and NaNO3. The filament temperature was found to be a key influencing factor in order to optimize the strength and Na–K deviation of the observed ion current. The ability to simultaneously report absolute concentrations of Na and K makes the instrument attractive for solid fuel conversion of alkali-rich fuels such as low-grade biomass and to explore behavior deviations of Na and K in high temperature processes.