This study deals with the valorization of Algerian date palm fronds (DPF) as a prominent alternative biomass for the synthesis of energy-rich cellulosic biopolymers through electrophilic nitration of the isolated pristine cellulose and cellulose microcrystals (OCN and MCCN). The successful chemical structure of the designed energetic biopolymers and their cellulosic precursors was confirmed by Fourier trans-form infrared spectroscopy (FTIR) analysis. Furthermore, differential scanning calorimetry (DSC) indicated that the new produced MCCN present slightly lower thermal stability than the common OCN. In addition, elevated density and great nitrogen content were obtained for MCCN compared to the conventional OCN. Consequently, the explored DPF could be considered as a valuable alternative non-woody biomass for the production of advanced high-energy cellulosic biopolymers for potential application in the next generation of solid propellant formulations.