In this research,a promising class of insensitive and high-energy dense biopolymers,which contain nitrogen-rich 1H-tetrazol-1-yl acetate and nitrate ester functional groups,was successfully synthesized through tetrazole derivatization and nitration of cellulose and its micro-sized derivative(TNCN and TCMCN).Their molecular structures,physicochemical properties,thermal behaviors,mechanical sensi-tivities and detonation performances were studied and compared to those of the corresponding nitro-cellulose and nitrated micro-sized cellulose(NCN and CMCN).The developed energetic TNCN and TCMCN exhibited insensitive character with excellent features such as density of 1.710 g/cm3 and 1.726 g/cm3,nitrogen content of 20.95％and 22.59％,and detonation velocity of 7552 m/s and 7786 m/s,respectively,and thereby demonstrate their potential applications as new generation of energetic bio-polymers to substitute the common NCN.Furthermore,thermal results showed that the designed nitrated and chemical modified cellulosic biopolymers displayed good thermal stability with multistep decomposition mechanism.These results enrich future prospects for the design of promising insensitive and high-energy dense cellulose-rich materials and commence a new chapter in this field.