The anodization reaction of 6H-SiC using HF solution was investigated to understand the formation of porous SiC. The anodization reaction proceeds via two Stages in which the oxidation of:SIC is followed by the removal of SiO by fluorine ions. The microstructure of porous SiC changes fi om fibrous-to dendritic as the anodization current is increased, and also shows other transitional morphology. The photoluminescence of these porous SiC with different microstructures was also investigated, and the photoluminescence band of higher energy was found to become enhanced as the microstructure of porous SiC changed from fibrous to porous dendritic.