Studies have shown the existence of macro- and microscopic level structure and property variations among cocoon shells and fibers from mulberry and wild silkworms. Narumi et al. [7] revealed the presence of a large number of voids in the cross-sections of wild silk fibers in contrast to mulberry silk. The silk fibers from the wild silkmoths have many longitudinal striations on their surface and are porous which make them lighter than mulberry silk [8]. Wild silk fibers also consist of flattened, ribbon-like filaments of much greater diameter than mulberry silk [9]. Although the potential of African wild silkmoths for production of large cocoons with economic importance has been documented, the microscopic structure and properties of these fibers and cocoon shells have not been studied in detail. Comprehensive studies of such structures will lead to better understanding of the cocoon spinning behaviour of the silkworms and how silk fibers are arranged in the cocoon shells to suit their designed purposes. This information would be of immense value in the prudent evaluation of the potential of silks for commercial application and further investigate the structure–property–function relations of silk fibers and cocoon shells. In this study, we investigate the surface and cross-sectional structures of silk fibers and cocoon shells produced by four species of wild silkmoths using scanning electron microscope (SEM) and Fourier transform infrared (FTIR) spectroscopy.