The globin gene superfamily has been well characterised in vertebrates, however, there has been limited research in early diverging lineages, such as phylum Cnidaria. This study aimed to identify globin genes in multiple cnidarian lineages, and to characterise the evolution, structure and expression of these genes. Bioinformatic approaches were used to identify globin genes, and to determine the protein structures and expression patterns for these genes. Analyses have shown that all cnidarians possess neuroglobin-like (Ngb-like) genes. Furthermore, actiniarians have undergone a large-scale expansion of Ngb-like genes with a hexacoordinate conformation, as well as, a neofunctionalisation event resulting in a single lineage of pentacoordinate Ngb-like gene. Some Ngb-like genes displayed tissue and development specific expression with very few orthologous genes similarly expressed across species. Overall our analyses suggest that a Ngb-like gene was probably the ancestral globin gene present in the last common ancestor of eumetazoans. The identification of a large-scale expansion and neofunctionalisation of Ngb-like genes in actiniarians provides an excellent starting point to further our understanding of the evolution and function of the globin gene superfamily.