Dry reforming of methane (DRM) was investigated using nanostructured core@shell materials, thermally activated with two different heating methods, namely conventional resistive heating and microwave. The core@shell catalysts were composed of β-SiC nanoparticles, with a mean particle size below 100 nm, coated by a uniform SiO2 shell of ca. 30 nm thickness. Highly dispersed Rh nanoparticles, with a mean particle size of 2.5 nm, were present on the surface of the SiO2 shell. Operation under microwave heating conditions enhanced the reverse water gas shift reaction activity, which takes place in parallel with the DRM process, as compared to the operation under resistive heating conditions. Moreover, stable long-term operation was achieved under microwaved-assisted conditions, due to the unique spatial arrangement of the phases composing the nanostructured catalytic system, together with the suppression of irreversible coke deposition.