Organic resorcinol formaldehyde (RF) sol was electrosprayed to form RF nanodroplets which were collected on a Si wafer. After oven drying at 60°C for 12 hours, RF nano-droplets were pyrolyzed at 900°C in an inert atmosphere to yield the carbon nanospheres. This study reports the optimization of various process parameters including needle diameter, applied electric potential and liquid flow rate in order to get spherical, mono-disperse particles. For the organic RF sol, the optimized parameters, needle diameter 0.241 mm, electric potential 1.5 kV/cm and a flow rate of 0.8 ml/h, enabled the synthesis of nearly monodisperse carbon nano-spheres with diameter of 30.2 ± 7.1 nm. Water contact angle (WCA) studies revealed that the surface properties were significantly influenced by the surface morphologies. The surface covered with the RF derived carbon nano-spheres was super hydrophilic (WCA 10.1°) as compared to a mild hydrophilic nature of the RF derived smooth carbon films (WCA 83.3°). The electrosprayed carbon nanospheres synthesized here may find potential applications as adsorbents and drug carriers, and in carbon-based microelectromechanical systems (C-MEMS) including bio-MEMS.