The role of surfactants on carbon cryogels is investigated by using three different surfactants, nonionic (SPAN80), cationic (trimethylstearylammonium chloride; C18) and nonionic polymeric fluorinated (FC4430) surfactants. By using different SPAN80 concentrations (10.0, 5.0, 2.5, 1.0 and 0.5 vol.%), double-structure carbon microspheres with S BET (630–700 m 2/g) and V mes (0.51–0.93 cm 3/g) are obtained. Mesoporous carbon cryogels with different S BET and V mes are prepared by using C18 with different volume ratios of cyclohexane to water in a C18/water/cyclohexane mixture. Carbon cryogels with S BET (690–810 m 2/g) and V mes (0.83–1.74 cm 3/g) are obtained when cyclohexane is contained in the mixture, on the contrary, when there is no cyclohexane in the mixture, a water-based carbon cryogel with low S BET (480 m 2/g) and V mes (0.29 cm 3/g) is obtained. Carbon cryogels prepared by using C18 have larger mesopore size and broader mesopore size distribution compared with carbon cryogels prepared by using other surfactants. Microcellular (sponge-like) carbon cryogels with mesoporous surface, S BET (210–660 m 2/g) and V mes (0.37–0.92 cm 3/g), are obtained by introducing FC4430 (two concentrations) to two starting RF solutions (C/W=6,45). Low FC4430 concentration leads to carbon cryogels with higher S BET (610 and 660 m 2/g) and narrower mesopore size distributions compared to the high concentration counterpart. Hence, it is found that different surfactant types have interesting effects on morphologies and porous properties of RF carbon cryogels.