The immobilization of suspension catalysts in flexible, fibrillated films offers a promising solution to the mass transfer limitations often encountered in three-phase hydrogenation reactions. This study investigates the catalytic performance and mass transfer properties of fibrillated films in the hydrogenation of nitrobenzene to aniline, comparing them to free-flowing powdered catalysts. Fibrillated films were prepared from Pd/C catalysts with varying thicknesses (100–400 µm), and their performance was evaluated through kinetic studies in both batch reactors and microreactors. The specific activity of the films was significantly influenced by film thickness with thinner films demonstrating lower mass transfer limitations. However, mass transfer limitations were observed in thicker films, prompting the development of alternative film designs, including enhanced macro-porous films and sandwich structures. These modifications successfully minimized diffusion limitations, achieving similar specific activity to the powder catalysts while maintaining the mechanical stability of the films. This work demonstrates the feasibility of using fibrillated films for continuous catalytic processes and highlights their potential for efficient catalyst reuse, avoiding filtration steps and enhancing process sustainability. Furthermore, while PTFE remains indispensable for producing such films due to its mechanical and thermal stability, ongoing research focuses on identifying more environmentally friendly alternatives without compromising performance.