Polybenzoxazine has been successfully synthesized by a facile quasi-solventless method and used as a precursor for producing carbon xerogels via an ambient drying method, rather than usually used CO2 critical or freeze drying. In this work, we aim to study the effect of non-ionic (Synperonic NP30) and cationic (CTAB) surfactants on porous structure of polybenzoxazine-based carbon xerogels. Of particular interest is the formation of inter-connected structure of mesoporous carbon xerogels with mesopore diameters in the range of 15-36 nm by using different concentrations of the cationic surfactant. In addition, carbon xerogel nanospheres with the size of 50-200 nm are also obtained through the emulsion process. The mesopore diameters start to decrease when the carbon xerogel nanospheres are formed at the cationic surfactant concentration of equal to or exceeding 0.030 M. By using the non-ionic surfactant, the properties of the obtained carbon xerogels are shifted from mesoporous materials for the reference carbon xerogel (no surfactant added) to microporous materials at higher concentrations of the non-ionic surfactant (0.009-0.180 M). The carbon xerogel microspheres with the diameter size of about 2.51.tm are also obtained through the emulsion process when the concentration of the non-ionic surfactant is at 0.180 M. (C) 2015 Elsevier Inc. All rights reserved.