We report the influence of the native amorphous SiO(2) shell on the cathodoluminescence emission of 3C-SiC/SiO(2) core/shell nanowires. A shell-induced enhancement of the SiC near-band-edge emission is observed and studied as a function of the silicon dioxide thickness. Since the diameter of the investigated SiC cores rules out any direct bandgap optical transitions due to confinement effects, this enhancement is ascribed to a carrier diffusion from the shell to the core, promoted by the alignment of the SiO(2) and SiC bands in a type I quantum well. An accurate correlation between the optical emission and structural and SiO(2)-SiC interface properties is also reported.