The potential syntheses of pure nitrogen materials may involve photolysis of azide compounds. In this work, compressed solid samples of NaN3 were photolyzed in gem anvil cells at pressures up to 5.0 GPa. Reaction rates and mechanisms for the photolytic processes were studied using single-shot time-resolved (microsecond scale) absorption spectroscopy. Two broad absorption bands due to reaction intermediates were observed at 300 and 700 nm. Tentative assignments of the reaction intermediates and their reaction rates were used to help elucidate the potential for high-pressure syntheses of novel nitrogen structures. Finally, recovered products were analyzed with infrared and Raman vibrational spectroscopy.