Phosphorus-rich biomass can cause operational problems in combustion units. Na-phytate, a model compound used to simulate phosphorus in biomass, was studied in a laboratory-scale reactor under temperature and gas atmosphere conditions relevant for pyrolysis, combustion, and gasification in fixed bed or fluidized bed reactors to understand the P and Na release behavior. Solid residues from Na-phytate thermal conversion were analyzed using ICP with optical emission spectrometry in order to quantify the P and Na release. The release mechanism was evaluated based on FTIR spectroscopy analysis of the residues, measurement of the flue gas CO/CO2 concentration, characterization of flue gas particles using SEM with EDS, and thermodynamic equilibrium calculations. Na-phytate decomposed in several steps under a nitrogen atmosphere, starting with condensation of the phosphate OH groups, followed by carbonization in the temperature range 300–420 °C. In the carbonization process, the phosphate units detached from the carbon structure and formed cyclic NaPO3. Above 800 °C, the C in the char reacted with the melted NaPO3 to form CO and gaseous elemental P. When the char produced from flash pyrolysis of Na-phytate at 800 °C for 10 min was exposed to 1% O2, 10% CO2, or 10% H2O (in N2), the release of Na and P to the gas phase in the temperature range 800–1000 °C was around 0–7%. However, the release of P in an inert atmosphere, with a holding time of 2 h or until full char conversion had been achieved, increased from around 4% at 800 °C to almost 30% at 1000 °C. The results indicated that carbothermic reduction reaction is responsible for the release of P and that NaPO3 vaporization is not the dominating mechanism for P and Na release at temperatures below 1000 °C. A small amount of P was released in the O2, CO2, and H2O containing gases because these gas species consumed the char and thereby inhibited the release of P.