In the frame of developing new high-energy materials from bioresources, emergent cellulose and microcrystalline cellulose functionalized with explosophoric azides were successfully synthesized from a prominent alternative esparto grass fibres. The designed insensitive nitrogen-rich cellulosic biopolymers, namely, azidodeoxy esparto grass cellulose (AEGC) and azidodeoxy esparto grass microcrystalline cellulose (AEGMCC), displayed outstanding features, such as nitrogen content (w/w) of 18.24-18.68 %, the density of 1.601-1.626 g/cm 3 , and thermal decomposition of 203-218 °C. Their kinetic triplet was also determined under non-isothermal DSC conditions employing isonversional integral approaches. Interestingly, the appa-rent activation energy and the decimal logarithm of a preexponential factor of the developed AEGC and AEGMCC were found to be better than those of the common nitrocellulose. In addition, the reaction model examination based on Trache-Abdelaziz-Siwani (TAS) approach revealed that the produced AEGC and AEGMCC were accurately presented by an autocatalytic Avrami-Erofeev decomposition process. These results established that esparto grass fibres could be considered as a valuable alternative feedstock for the synthesis of outstanding energetic cellulose-rich polymers for potential applications in solid propellant formulations.