Carbon nanospheres were synthesized using sol–gel processing of organic and aqueous resorcinol formaldehyde (RF) sols combined with electrospraying technique. RF sol was electrosprayed to form nanodroplets which were collected on a Si wafer. After oven drying at 60°C for 12 h, 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 monodispersed carbon nano-spheres with diameter of 30.2 ± 7.1 nm. With the same conditions, aqueous RF sol produced irregularly shaped nanoparticles with a smaller mean diameter and much higher variance (17.4 ± 8.0 nm). The surface properties were significantly influenced by the surface morphologies as demonstrated by the water contact angle (WCA) studies. The surface covered with the RF derived carbon nano-spheres was extremely hydrophilic (WCA 10.1°) as compared to a much weaker hydrophilicity of the RF derived carbon films (WCA 83.3°). The hydrophilic carbon nanospheres reported here may have potential applications as adsorbents and in controlled drug delivery, biosensors and carbon-based microelectromechanical systems (C-MEMS) including bio-MEMS.