Efficacy of a new approach for the synthesis of graphene oxide (GO) nanosheets that has been recently reported (Ogino et al. in Chem Mater 26:3334-3339, 2014) was investigated further using graphite oxides with various degrees of oxidation and average particle sizes. The approach consists of rapid freeze-thaw cycles of water containing graphite oxide, which enables the efficient exfoliation of graphite oxide layers with the minimal fragmentation of GO sheets. The method is effective for the exfoliation of graphite oxides with C/O atomic ratios <= 2.6 as shown by experiments with various degrees of oxidation of graphite oxides. When this method was tested for large particle-size graphite oxide that had been prepared from graphite with the average particle size of 60 mu m, it formed approximately tenfold larger GO sheets than those prepared using sonication. Exfoliation experiments conducted at different freezing rates of water demonstrate that a faster freezing rate of water yielded a higher concentration of a dispersed GO solution. Thus, the results support the hypothesis that rapid phase change enables efficient layer exfoliation.