The self-assembly and phase behavior of cellulose nanocrystals (CNCs) in binary liquid mixtures of ethylene-glycol (EG):water was investigated. Our findings indicate that a small fraction of water delays the onset of colloidal jammed states previously reported in water-free organic solvents. Here the full phase diagram of CNCs evolves, including the chiral nematic phase (N*), characterized by long-range orientational order and non-isotropic macroscopic properties. Furthermore, the effect of the solvent-mixture composition on the properties of the CNC mesophases is found to be scale-dependent: the micron-size pitch of the N* phase decreases as the dielectric constant (ε_r) of the solvent mixture is reduced (higher EG content). Yet the nanometric inter-particle spacing of the CNC rods (measured using SAXS and cryo-TEM) is almost independent on the EG content. Also, unlike theoretical predictions, the transition to the biphasic regime is not sensitive to ε_r of the solvent mixtures and takes place at a higher CNC volume fraction than in aqueous suspensions. These observations may be rationalized by hypothesizing that vicinal water, adsorbed at the CNC surface, prevents kinetic arrest, and dictates the local dielectric constant and thus the effective diameter of the rods (via the Debye length), while ε_r of the liquid-mixture dominates the pitch length (micron scale) and the optical properties. These findings indicate that the water content of EG:water mixtures may be used for engineering colloidal inks where delayed kinetic arrest and jamming of the CNCs enable printing and casting of tunable, optically-active thin films and coatings.