Summary: Heparin, a potent anticoagulant, has been used for the first time for the synthesis of PPy nanowires serving not only as an anion dopant but also as an effective morphology‐directing agent. The obtained PPy nanowires exhibit long and fine structures with smooth surface and the average diameter of the nanowires is about 90–100 nm and lengths are several hundred nanometers to micrometers. The possible formation mechanism of PPy nanowires may be related to the chain structure of heparin with functional groups ( SO and COO−) on the surface. The effect of concentrations of pyrrole monomers and heparin on the morphology and size of PPy nanowires has been investigated.