Cellulose nanofibril (CNF) films were prepared from side streams generated by the sugarcane industry, that is, bagasse. Two fractionation processes were utilized for comparison purposes: (1) soda and (2) hot water and soda pretreatments. 2,2,6,6-Tetramethylpiperidinyl-1-oxyl-mediated oxidation was applied to facilitate the nanofibrillation of the bagasse fibers. Poly(ethylene glycol) (PEG) was chosen as plasticizer to improve the ductility of CNF films. The neat CNF and biocomposite films (CNF and 40% PEG) were used for fabrication of self-standing humidity sensors. CNF-based humidity sensors exhibited high change of impedance, within four orders of magnitude, in response to relative humidity (RH) from 20 to 90%. The use of plasticizer had an impact on sensor kinetics. While the biocomposite film sensors showed slightly longer response time, the recovery time of these plasticized sensors was two times shorter in comparison to sensors without PEG. This study demonstrated that agroindustrial side streams can form the basis for high-end applications such as humidity sensors, with potential for, for example, packaging and wound dressing applications.