Porous carbon with pores and porewalls was prepared by the polymerization of an O/W emulsion of Span 80-Tween 80/liquid paraffin/water resorcinol formaldehyde (R/F) with NaOH. However, a different kind of carbon material which comprises spherical or intertwined worm-like particles was fabricated by using ammonia as the catalyst. Inferential evidence indicates that the O/W emulsion undergoes a phase inversion caused by ammonia; whether the phase inversion leading to a W/O emulsion or a transition structure depends on the R/F concentration within the aqueous phase.