SiC hexagonal nanoprisms have been prepared by a reaction of multiwall carbon nanotubes and Si vapor in an Astro furnace at 1450 °C for 3 h. The polytype, morphology, crystal structure of the nanoprisms were studied by X-ray powder diffraction, scanning electron microscopy and high resolution transmission electron microscopy, showing their hexagonal nanoprism shapes with a 3C-SiC single crystal structure with a diameter of about 100 nm and 2 μm in length. The photoluminescence spectrum of the nanoprisms exhibits a significant blue-shift relative to bulk 3C-SiC and other nanostructured SiC. The possible growth mechanism that controls the nanostructure formation is also analysed.