The development of efficient thermo-osmotic energy conversion devices has fascinated scientists and engineers for several decades in terms of satisfying the growing energy demand. The fabrication of ionic membranes with a high charge population is known to be a critical factor in the design of high-performance power generators for achieving high permselectivity and, consequently, high power extraction efficiency. Herein, we experimentally demonstrated that the thermo-osmotic energy conversion efficiency was improved by increasing the membrane charge density; however, this enhancement occurred only within a narrow window and subsequently exhibited a plateau over a threshold density. The complex interplay between pore−pore interactions and fluid structuration for ion transport across the upscaled nanoporous membranes helped explain the obtained results with the aid of numerical simulations. Consequently, the power generation efficiency of the multipore membrane deteriorated, deviating considerably from the case of simple linear extrapolation of the behavior of the single-pore counterparts. A plateau in the output electric power was observed at a moderate charge density, affording a value of 210 W m−2 at a 50-fold salinity difference with a temperature gradient of 40 K. This study has far-reaching implications for discerning an optimal range of membrane charge populations for augmenting the energy extraction, rather than intuitively focusing on achieving high densities.