Energy harvesting has become a crucial technology for sustainable energy solutions; in particular, the utilization of ambient water movement in hydrovoltaic generators has emerged as a promising approach. However, optimizing performance requires an understanding of structural factors affecting energy harvesting, particularly capillary effects. This study aimed to improve hydrovoltaic generator performance by adjusting internal fiber density, which influences water transport and ion mobility. Using cold isostatic pressing, cellulose acetate (CA) loading in a urethane mold was varied to optimize internal density. As CA loading increased, the fiber arrangement became denser, narrowing capillary pathways and reducing proton mobility. While open-circuit voltage (VOC) remained stable, short-circuit current (ISC) decreased with higher CA mass. The sample with a loading of 0.3 g exhibited the highest energy harvesting efficiency, achieving ISC = 107.2 μA, VOC = 0.15 V, and power (P) = 16.7 μW. This study provides insights into methods of improving hydrovoltaic generator efficiency through internal structural modifications.