Cellulose is the most abundant renewable material in nature. In this work, ordered cellulose nanocrystals (CNCs) have been transformed into porous carbon with an increased short-range ordered lattice and percolated carbon nanofiber at a relatively low carbonization temperature of 1000°C. When evaluated as anode for sodium-ion batteries (SIBs), the CNC derived porous carbon shows superior performances including a high reversible capacity of 340mAh/g at a current density of 100mA/g, which is one of the highest capacity carbon anodes for SIBs. Moreover, the rate capability and cycling stability of the porous carbon are also excellent. The excellent electrochemical performance is attributed to the larger interlayer spacing, porous structure, and high electrical conductivity arising from the ordered carbon lattice and the percolated carbon nanofiber. The formation of nano-sized graphitic carbon from the ordered CNC at the low carbonization temperature of 1000°C is supported by both molecular dynamic simulations and as well as in-situ TEM measurements. This study shed light on the fundamental understanding of converting hydrocarbon biopolymer from wood to high quality carbon with a large domain of ordered lattice.