Although important, very little has been demonstrated in the literature to experimentally demonstrate the effects of porosities and pore size on the evaporation flux in polymeric membranes. Additionally, we suspect that a batch-mode setup, i.e., stagnant water, could cause a build-up of heat in the system, influencing the evaporation mass-flux mechanism, and jeopardizing the ability to attain a real correlation between evaporation and effects of pore characteristics. Herein, we fabricate polyvinylidene fluoride membranes containing variable amounts of a Fumed Silica additive to achieve membranes with variable properties, and we investigate the change in the performance of the solar-assisted thin-film evaporation utilizing an in-house built continuous flow evaporation setup (to avoid heat build-up effects in the bulk of the water and demonstrate a continuous flow system). Our membrane design approach had two important advantages: (1) the achievement of similar heat transfer and solar absorbance properties and (2) the achievement of variable pore sizes and volume porosities. We show that the mass flux increased as the mean pore size decreased, indicating that the mode of mass transfer occurred due to the thin-film region of the meniscus from the small fluid velocities near the interface, and we attribute the results to the increase in the capillary pumping effects through the mesoporous channels as they get thinner.