The subtle control on the self-assembly behavior of graphene oxide (GO) nanosheets is one of effective ways for the preparation of high-performance macroscopic graphene-based materials. In this work, detailed characterizations and discussion on the morphological and compositional changes on the solid products in various alcohol-water dispersions of GO under gamma-ray radiation were carried out, proving the concurrent hydroxyalkylation and reduction processes of GO nanosheets in the system, which triggered the spontaneous self-assembly of the hydroxyalkylated and reduced GO nanosheets (HA-rGO). The pH and the volume ratio of alcohol to water (phi(a/w)) are the key factors to control the self-assembly of the HA-rGO sheets. A free-standing graphene hydrogel (GH) only forms in the strong acid alcohol-water media with an appropriate phi(a/w). After the freeze-drying of the GH, a macroporous graphene aerogel (GA) was obtained, which exhibited a high absorption performance for not only nonpolar molecules (cyclohexane and kerosene), but also most polar molecules (toluene, chloroform, glycol, etc). This work demonstrates a comprehensive self-assembly mechanism of GO nanosheets in an aqueous media under gamma-ray radiation and reveals that GA produced from the reduction of GO can be used as potential super-adsorbents for not only waste oil, but also the polar alcohols. (C) 2017 Elsevier B.V. All rights reserved.