Combination of sol–gel and sonochemical techniques is suggested for producing a nanostructured graphene–alumina hybrid, which is a promising raw material for manufacturing fine-grained ceramics. This study focuses on the use of dodecylamine both in the sol–gel synthesis of Al-containing particles and in sonochemical graphene exfoliation. It has been shown that, when forming graphene–alumina composite in a reaction mixture of Al-containing sol and graphene suspension, graphene sheets take part as a template in the formation of a hybrid structure. Graphene sheets orient sol particles on their surface due to van der Waals interaction and control growth and direction of oligomeric gel chains. The graphene sheets limit the growth of Al-containing particles, which leads to an increase in the specific surface of the hybrid as compared to an alumina powder sourced from the same sol. The proposed approach enables the preparation of chemically homogeneous composite nanopowders with uniform distribution of components. © 2020 Taylor & Francis Group, LLC.