Bioderived cellulose nanocrystals (CNCs) are used to create light, flexible, biocompatible, and biodegradable electronic devices. Herein, surface modification of cellulose nanocrystals was employed to fabricate cationic and anionic CNCs. Subsequently, we demonstrated rectification behavior from a fixed junction between two agarose hydrogels doped with cationic and anionic cellulose nanocrystals. The current rectification ratio reaches 70 reproducibly, which is significantly higher than that for analogous diodes generated with microfibrillated cellulose (∼15) and the first polyelectrolyte gel diode (∼40). The current−voltage characteristics of the CNC−hydrogel diode are influenced by concentration, gel thickness, scanning frequency, and applied voltage. The high surface area of CNC resulted in high charge density after surface modification, which in turn resulted in good rectification behavior from only small amounts of dopant material.