Micro-TATB particles with different sizes and 3D nanoporous TATB architectures with different specific surface areas were prepared through recrystallization to study short pulse duration shock initiation properties by electric gun technology. For micro-TATB, the initiation threshold significantly decreases with TATB average size ranging from 79.7μm to 0.5μm. For 3D nanoporous TATB architecture, the initiation threshold decreases and then increases with specific surface areas increased from 9.6 m2/g to 36.2 m2/g. The lowest initiation thresholds are obtained for the micro-TATB with average sizes of 1.3μm and 0.5μm, and 3D nanoporous TATB architecture with specific surface area of 22.4 m2/g. The shock initiation thresholds of micro-TATB and 3D nanoporous TATB architectures show significantly decreases with the porosity increased. The decomposition reaction and thermal conductivity properties were further investigated to understand the initial response mechanism. High porosity provides more collapse sites to generate high temperature for formation of hot spots. The low thermal conductivity and decomposition temperature could enhance the formation and ignition of the hot spots, and initial decomposition reaction of TATB. The effect of the decomposition temperature is higher than that of the thermal conductivity on the shock initiation properties. The enhanced decomposition reaction could promote energy release and transfer process from the ignition to the combustion. This work offers a new insight to understand the effects of microstructure on the shock initiation properties and the initial response mechanism of TATB.