Liquid crystalline (LC) behaviors of cellulose nanocrystal (CNC), derived from wood, cotton or other cellulose-based biopolymers, have been actively investigated due to their unique optical properties and their superb mechanical properties, which open up potential applications in bioelectronics and biomedical engineering. In particular, many attempts have been made to control phase and orientation of LC-CNCs because they are critical factors deciding optical and mechanical properties, and electromechanical performances. Through the applications of mechanical force, electric field and magnetic field, some degree of success has been achieved; however, realizing homogeneous arrangements of CNCs that can be exploited at the macroscale is still elusive, owing to a variety of intermolecular interactions. The characterizations of the LC phase and orientation of CNCs are also challenging due to their complex biological structures. In this report, we introduce approaches to control the phase and orientation of LC-CNCs through the self-assembly, mechanical force and electric field. The liquid crystalline behaviors of CNCs in polar solvents and at the air/water interface are discussed. Translational and rotational behaviors of CNCs under DC electric field are also investigated as a function of their surface charge and dipole moment. In addition, we introduce a nonlinear optical process, namely, sum frequency generation (SFG) spectroscopy, for the structural characterization of LC-CNCs. Using SFG, we can analyze not only crystal phase and structure, but also polar ordering of CNCs which plays a key role in determining their electromechanical performances. Development of cellulose-based smart materials will expand the spectrum of available functional materials that are lightweight, flexible, mechanically tough, and thermally stable at moderately high temperatures (up to 300oC).