The high mechanical strength, large specific surface area, favorable biocompatibility, and degradability of nanocellulose (CNC) enable it to be a potential alternative to petroleum-based materials. However, the traditional preparation of CNCs requires a large amount of strong acid, which poses a serious challenge to equipment maintenance, waste liquid recycling, and economics. In this study, a solid and easily recoverable zirconium phosphate (ZrP) was used to assist in the phosphoric acid co-catalyzed hydrolysis of lignocellulose for extracting CNCs. Due to the presence of acidic phosphate groups, ZrP has a strong active center with a high catalytic activity. With the assistance of ZrP, the amount of phosphoric acid used in the reaction is significantly reduced, improving the equipment's durability and economic efficiency. The effects of the process conditions investigated were the phosphate acid concentration, reaction temperature, and reaction time on the yield of CNCs. The Box-Behnken design (BBD) method from the response surface methodology (RSM) was applied to investigate and optimize the preparation conditions. The optimized pre-treatment conditions were 49.27% phosphoric acid concentration, 65.38 °C reaction temperature, and 5 h reaction time with a maximal cellulose yield (48.33%). The obtained CNCs show a granular shape with a length of 4050 nm and a diameter of 2030 nm, while its high zeta potential (-24.5 mV) make CNCs present a stable dispersion in aqueous media. Moreover, CNCs have a high crystallinity of 78.70% within the crystal type of cellulose Ⅰ. As such, this study may pioneer the horizon for developing a green method for the efficient preparation of CNC, and it is of great significance for CNCs practical production process.