The mechanical and thermo-mechanical properties of polybenzoxazine nanocomposites containing multi-walled carbon nanotubes (MWCNTs) functionalized with surfactant are studied. The results are specifically compared with the corresponding properties of epoxy-based nanocomposites. The CNTs bring about significant improvements in flexural strength, flexural modulus, storage modulus and glass transition temperature, T g, of CNT/polybenzoxazine nanocomposites at the expense of impact fracture toughness. The surfactant treatment has a beneficial effect on the improvement of these properties, except the impact toughness, through enhanced CNT dispersion and interfacial interaction. The former four properties are in general higher for the CNT/polybenzoxazine nanocomposites than the epoxy counterparts, and vice versa for the impact toughness. The addition of CNTs has an ameliorating effect of lowering the coefficient of thermal expansion (CTE) of polybenzoxazine nanocomposites in both the regions below and above T g, whereas the reverse is true for the epoxy nanocomposites. This observation has a particular implication of exploiting the CNT/polybenzoxazine nanocomposites in applications requiring low shrinkage and accurate dimensional control. © 2012 Elsevier Ltd.