Potassium (K) is one of the main and most hazardous trace species released to the gas-phase during thermochemical conversion of biomass. Accurate experimental data and models of K release are needed to better understand the chemistry involved. Tunable diode laser absorption spectroscopy (TDLAS) is used for simultaneous real-time in situ measurements of gas-phase atomic K, water (H2O) and gas temperature in the vicinity (boundary layer) of biomass particles during combustion in a laboratory single-particle reactor. Atomic K is detected in a wide dynamic range, including optically thick conditions, using direct absorption spectroscopy at the wavelength of 770 nm, while H2O and temperature are determined by calibration-free scanned wavelength modulation spectroscopy at 1398 nm. The high accuracy and repeatability of the setup allows to distinguish measurements with varying initial particle mass, laser beam height above the particle and fuel type. Four types of biomass with different ash composition are investigated: softwood, Salix, Miscanthus and wheat straw. For Salix and wheat straw, the K release behaviour is, for the first time, compared to a detailed numerical particle model taking into account the interaction between K/S/Cl composition in the particle ash. A good agreement is achieved between the measured and calculated time-resolved atomic K concentrations for the devolatilization phase of the biomass particles.