To study the structure and performance of NC/GAP printed samples， nitrocellulose （NC） and glycidyl azide polymer （GAP） were used as raw materials to prepare NC/GAP printed samples with GAP mass fractions ranging from 0% to 30% via 3D printing. The structure， thermal stability， combustion performance and mechanical properties of NC/GAP composites were characterized by field-emission scanning electron microscopy （FE-SEM）， fourier transform infrared spectroscopy （FT-IR）， differential scanning calorimetry （DSC）， high-speed camera， oxygen bomb calorimeter and universal tensile testing instrument. Results show that the NC/GAP printed samples have regular morphologies， with no obvious interface between the internal layers. With the increasing of GAP content， the thermal stability gradually enhances， the compatibility between NC and GAP gradually deteriorates， the tensile strength gradually decreases， and the combustion rate shows a trend of first increasing and then decreasing. When the mass fraction of GAP is 10%， the maximum combustion rate reaches 25.6 mm·s^-1， which is 46% higher than that of NC. When the mass fraction of GAP increases from 0% to 30%， the heat of combustion in air and argon increase from 2843.2 J·g^-1 to 5260.1 J·g^-1 and 1065.7 J·g^-1 to 1938.7 J·g^-1， increasing by 85% and 82%， respectively.