An instrument for on-line measurements of alkali components in hot flue gas streams is presented. The instrument is based on surface ionization technique and is equipped with a hot sampling line used to extract flue gas for continuous alkali measurements at pressures up to 30 bar. The instrument, its support system and the calibration procedure is described. Field campaigns with the instrument have been performed at fluidized-bed combustion facilities operating under pressurized and atmospheric conditions and using several fuels, including coal, biomass, and demolition waste. The instrument performance has been satisfactory both during pressurized circulating fluidized-bed coal combustion with alkali concentrations downstream of a hot gas filter in the ppb range, and in particle-laden conditions with alkali levels up to about 10 ppm. The measured alkali concentration corresponds to the concentration of alkali components present as vapors and fine-mode particles. In systems with high levels of fluidized-bed material or fly ash, a contribution to the signal from alkali bound to coarse particles is also expected. Under these conditions, the instrument is suggested to be operated in a pulse counting mode where the concentration of coarse particles can be estimated. The instrument is concluded to provide a durable, sensitive, and reliable alkali measurement method with a high time resolution and with a lower detection limit of around 1 ppb, which should be suitable for a large range of applications.