A quantitative and simultaneous measurement of K, KCl, and KOH vapors from a burning fuel sample combusted in a single particle reactor was performed using collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) with a time resolution of 0.2 s. The previously presented CPFAAS technique was extended in this work to cover two consecutive fragmentation pulses for the photofragmentation of KCl and KOH. The spectral overlapping of the fragmentation spectra of KCl and KOH is discussed, and a linear equation system for the correction of the spectral interference is introduced. The detection limits for KCl, KOH, and K with the presented measurement arrangement and with 1 cm sample length were 0.5, 0.1, and 0.001 parts per million, respectively. The experimental setup was applied to analyze K, KCl, and KOH release from 10 mg spruce bark samples combusted at the temperatures of 850, 950, and 1050 °C with 10% of O2. The combustion experiments provided data on the form of K vapors and their release during different combustion phases and at different temperatures. The measured release histories agreed with earlier studies of K release. The simultaneous direct measurement of atomic K, KCl, and KOH will help in the impact of both the form of K in the biomass and fuel variables, such as particle size, on the release of K from biomass fuels.