Access to clean water is a global challenge, and fog collectors are a promising solution. Polycarbonate (PC) fibers have been used in fog collectors but with limited efficiency. In this study, we show that controlling voltage polarity and humidity during the electrospinning of PC fibers improves their surface properties for water collection capability. We experimentally measured the effect of both the surface morphology and the chemistry of PC fiber on their surface potential and mechanical properties in relation to the water collection efficiency from fog. PC fibers produced at high humidity and with negative voltage polarity show a superior water collection rate combined with the highest tensile strength. We proved that electric potential on surface and morphology are crucial, as often designed by nature, for enhancing the water collection capabilities via the single-step production of fibers without any postprocessing needs.