Carbon xerogel microspheres were synthesized by inverse emulsion polymerization of resorcinol with formaldehyde, followed by pyrolysis at 900 °C under nitrogen atmosphere. We have studied the effect of various synthesis parameters, including dilution ratio and hydrophilic-lipophilic balance (HLB) of nonionic surfactants, on the size and morphology of resulting structures. The average particle size of carbon microspheres could be modulated from 1 to 28 μm by varying the dilution ratio over 3 orders of magnitude. Increase in the HLB value and the amount of surfactants produced a variety of dense carbon, but open-architecture fractallike structures. Three different methods of stirring, namely, magnetic, mechanical, and ultrasonication were applied during the inverse emulsification to produce carbon xerogel microstructures. Formation of a wide spectrum of nonporous carbon particle morphologies, including the highly branched, hierarchical microparticles, by tuning the synthesis conditions may have potential applications in printing technology, controlled drug delivery, biosensors, and carbon-based microelectromechanical systems (C-MEMS) including bio-MEMS. © 2009 American Chemical Society.