Cellulose nanocrystals (CNCs), produced by the acid hydrolysis of wood, cotton or other cellulose-rich sources, constitute a renewable nanosized raw material with a broad range of envisaged uses: for example, in composites, cosmetics and medical devices. The intriguing ability of CNCs to self-organize into a chiral nematic (cholesteric) liquid crystal phase with a helical arrangement has attracted significant interest, resulting in much research effort, as this arrangement gives dried CNC films a photonic band gap. The films thus acquire attractive optical properties, creating possibilities for use in applications such as security papers and mirrorless lasing. In this critical review, we discuss the sensitive balance between glass formation and liquid crystal self-assembly that governs the formation of the desired helical structure. We show that several as yet unclarified observations-some constituting severe obstacles for applications of CNCs-may result from competition between the two phenomena. Moreover, by comparison with the corresponding self-assembly processes of other rod-like nanoparticles, for example, carbon nanotubes and fd virus particles, we outline how further liquid crystal ordering phenomena may be expected from CNCs if the suspension parameters can be better controlled. Alternative interpretations of some unexpected phenomena are provided, and topics for future research are identified, as are new potential application strategies. NPG Asia Materials (2014) 6, e80; doi:10.1038/am.2013.69; published online 10 January 2014Keywords: cholesteric; gel; glass; liquid crystal; nanocellulose; photonic crystal; self-assembly INTRODUCTION Nanomaterials based on renewable resources are attracting rapidly growing interest, both from a fundamental scientific point of view and from the perspective of developing novel structural and functional macroscopic materials. 1,2 Using nature-based nanomaterials offers ecological advantages, and the extraordinary mechanical performance and/or photonic crystal character of biological composites such as bone, nacre, wood, beetle scales and butterfly wings is also an important inspiration for the development of new multifunctional materials. [3][4][5] However, full utilization of the intrinsic properties of nanosized starting materials requires the development of robust and versatile synthetic and processing routes to control assembly over several length scales. [6][7][8] Cellulose, one of the most versatile and widely found biopolymers in nature, has been used by humans for millennia as a building material, an energy source, a component of clothing and for storing and sharing knowledge and culture. Today, cellulose materials are used in a wide range of applications, and the paper and pulp industry