Highly ordered polyaniline (PANI) nanorods were prepared by oxidative polymerization in the presence of sucrose stearate surfactant acting as a soft template and acetone as solvent. The polymerized PANI nanorods were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy, and X-ray diffraction (XRD). Results showed that the concentration of sucrose stearate exhibited a strong influence on nanorods diameters, surfaces, and also the crystallinity of PANI. The diameters and crystallinity increase remarkably with increasing the sucrose stearate concentration. A mechanism for the formation of nanorods is also proposed. The steric hindrance of sucrose stearate molecules and hydrogen bonds formed between sucrose stearate and anilium ions or oligomers molecules play an important part in the formation of PANI nanorods.