Our previously reported computational study of the decomposition pathways of triacetone triperoxide (TATP), 1, predicted that unlike most energetic materials, which involve self-combustion of fuel and oxidants, 1 decomposes via a thermoneutral, non-redox pathway that involves entropy burst. These predictions are now corroborated by time-resolved monitoring of deflagration or detonation of 1 using a fast video camera following initiation by a short pulse focused laser beam. While a fireball always accompanies the explosion of 1 under air, the formation of a fireball is totally prevented under a nitrogen atmosphere. These observations indicate that combustion of the gaseous primary products occurs as a secondary event only in the presence of exogenous oxygen. The composition of the product mixture was found to depend on the experimental conditions. With long pulse focused laser beam (150 μs at 1064 nm) at either 210 or 110 mJ, the small amounts of charcoal needed for initiation suggest that the energy required to initiate 1 by pulse laser is 4-10 mJ, much smaller than the energy required for initiation by either mechanical stress or electric discharge. This time-resolved study highlights the very unusual properties of the peroxide based explosives.