Cellulose nanocrystals(CNC) are a kind of sustainable nanoparticles from biomass. We reviewed their unique advantages in material applications due to their rod-like morphology and crystalline structure of biocompatible nanoparticles, as well as their dimension-related effects and multi-level ordered structure. Then, we mentioned the surface molecular engineering of CNC, including the structural, physical, and chemical properties of their surface, along with the reaction-modification method and steric effect on structure regulation. We further discussed the performance-improvement and functionalization methods based on controlling the interactions between materials in the multicomponent complex phase/system, along with the assembly-control methods on the chiral and achiral array of CNC for luminescence-enhanced optical anti-counterfeiting. In the end, we prospected the design, development, and construction methods of new CNC materials.