Polypyrrole (PPy) with photonic crystal structures were synthesized from Morpho butterfly wings using a two-step templating process. In the first step photonic crystal SiO2 butterfly wings were synthesized from Morpho butterfly wings and in the second step the SiO2 butterfly wings were used as templates for the replication of PPy butterfly wings using an in situ polymerization method. The SiO2 templates were then removed from the PPy butterfly wings using a HF solution. The hierarchical structures down to the nanometer level, especially the photonic crystal structures, were retained in the final PPy replicas, as evidenced directly by field-emission scanning electron microscope (FE-SEM) and transmission electron microscopy (TEM). The optical properties of the resultant PPy replicas were investigated using reflectance spectroscopy and the PPy replicas exhibit brilliant color due to Bragg diffraction through its ordered periodic structures. The preliminary biosensing application was investigated and it was found that the PPy replicas showed a much higher biological activity compared with PPy powders through their response to dopamine (DA), probably due to the hierarchical structures as well as controlled porosity inherited from Morpho butterfly wings. It is expected that our strategy will open up new avenues for the synthesis of functional polymers with photonic crystal structures, which may form applications as biosensors.