Biodegradable composites obtained by reinforcing thermoplastic starch (TPS) with lignocellulosic fibers show great potential, but their strong sensitivity to water still limits practical applications. Among possible reinforcements, Helianthus tuberosus (topinambur) represents an underutilized agricultural residue that has been scarcely explored in this context. In this work, we demonstrate for the first time that topinambur fiber can improve the water vapor barrier properties of cassava starch films, while also providing a detailed analysis of sorption isotherms and the humidity-dependent relationship between surface roughness and contact angle, aspects rarely addressed in previous studies. SEM revealed uniform fiber dispersion and integration. Water sorption kinetics showed that fiber addition reduces both hydration and sorption time constant, indicating lower water affinity and greater water mobility. Water sorption isotherms confirmed that fiber incorporation significantly alters overall hydration and water–matrix interactions, revealing reduced effective water solubility in films. Water vapor permeability also decreased with fiber addition, mainly due to decreased water solubility, rather than changes in water diffusivity. While fiber addition enhanced surface-water repellency across all humidity levels, roughness exhibited a humidity-dependent response FTIR analysis confirmed fiber–matrix compatibility and suggested new hydrogen bonding. Overall, these findings identify topinambur fiber as a novel reinforcement for designing biodegradable films with improved humidity resistance for agroecological applications.