Combustion research requires detailed localized information on the dynamic combustion conditions to improve the accuracy of the simulations and, hence, improve the performance of the combustion processes. We have applied chemical reaction kinetics of potassium to measure the local temperature and O2 concentration in flue gas. An excess of free atomic potassium is created in the measurement volume by a photofragmenting precursor molecule such as potassium chloride or KOH which are widely released from solid fuels. The decay of the induced potassium concentration is followed with an absorption measurement using a narrow-linewidth diode laser. The temperature and O2 concentration are solved from the decay curve features using equations obtained from calibration measurements in a temperature range of 800°C-1000°C and in O2 concentrations of 0.1%-21%. The local flue gas temperature and O2 concentration were recorded in real time during devolatilization, char burning, and ash cooking phases of combustion in a single-particle reactor with a 5 Hz repetition rate. The method can be further extended to other target species and applications where the chemical dynamics can be disturbed with photofragmentation.