As extinct animals that flourished during the Cambrian explosion, chancelloriids have a unique body plan lacking guts but with a flexible integument and a suite of star-shaped, hollow sclerites. Due to this body plan, along with the paucity of knowledge on sclerite biomineralization, the phylogenetic position of chancelloriids within the Metazoa is still controversial. Integration of analyses of diverse fossils from Cambrian stage 2 to the Wuliuan Stage of China and Australia indicates that chancelloriid sclerites possess an encasement-like organic layer and a fibrous aragonitic layer. The organic layer is inferred to be a specialized trait derived from the epidermal integument of the animal body. The sclerites were likely biomineralized by using the outer organic layer as a template to absorb cations and precipitate crystal nuclei, reflecting a strategy adopted by a range of eumetazoans with a developed epidermis. Therefore, the hypothesis that chancelloriids represent an epitheliozoan-grade animal and an early explorer of template-based biomineralization is supported.