Abstract Summary: Polypyrrole nanotubes with high electric conductivity and azo function have been fabricated in high yield via an in‐situ polymerization. During the process fibrillar complex of FeCl 3 and methyl orange (MO), acting as a reactive self‐degraded template, directed the growth of polypyrrole on its surface and promoted the assembly into hollow nanotubular structures. TEM image of uncompleted PPy nanotubes synthesized in MO solutions after reaction for 40 min. magnified image TEM image of uncompleted PPy nanotubes synthesized in MO solutions after reaction for 40 min.