The increase in consumer demand for more sustainable packaging materials represents an opportunity for biopolymers utilization as an alternative to reduce the environmental impact of plastics. Cellulose (C) and chitosan (CH) are attractive biopolymers for film production due to their high abundance, biodegradability and low toxicity. The objective of this work was to incorporate cellulose nanocrystals (NC) and C extracted from corn cobs in films added with chitosan and to evaluate their properties and biodegradability. The physicochemical (water vapor barrier, moisture content, water solubility and color) and mechanical properties of the films were evaluated. Component interactions using Fourier-transform infrared (FTIR) spectroscopy, surface topography by means of atomic force microscopy (AFM), biodegradability utilizing a fungal mixture and compostability by burying film discs in compost were also determined. The C-NC-CH compared to C-CH films presented a lower moisture content (17.19 ± 1.11% and 20.07 ± 1.01%; w/w, respectively) and water vapor permeability (g m−1 s−1 Pa−1 × 10−12: 1.05 ± 0.15 and 1.57 ± 0.10; w/w, respectively) associated with the NC addition. Significantly high roughness (Rq = 4.90 ± 0.98 nm) was observed in films added to NC, suggesting a decreased homogeneity. The biodegradability test showed larger fungal growth on C-CH films than on CH films (>60% and <10%, respectively) due to the antifungal properties of CH. C extracted from corn cobs resulted in a good option as an alternative packaging material, while the use of NC improved the luminosity and water barrier properties of C-CH films, promoting strong interactions due to hydrogen bonds.