This work was intended for the identification of markers that are found only in the spoiled red pepper powder. When analyzed by GC/MASS, the spoiled red pepper powder contains characteristic naphthalene derivatives, 1, 2, 3, 5, 6, 7, 8, 8α-octahydro-1, 8α-dimethyl-7-(1-methylethenyl)-naphthalene and 2-isopropenyl-4α,8-dimethyl- 1, 2, 3, 4, 4α, 5, 6, 8α-octahydronaphthalene,which have not found in the normal red pepper powder. In addition, microscopic observation and microbial enumeration of the red pepper powder had been performed. Images by scanning electron microscopy showed that the surfaces of spoiled pepper powder were rough with many kinds of microbes, compared with those of normal red pepper powder. A good correlation between the bacterial and fungal counts in the same sample was observed and could be clearly classified into two groups, the normal and the spoiled group, by difference in the microbial counts. These results suggest that the spoiled red pepper powder can be identified by a combination of GC/MASS, microbial counts, and scanning electron microscopy.