This research demonstrated that polymerization of aniline on cellulose produces chiroptically active composites. Polymerization of aniline in the presence of cotton fibers consisting of chiral cellulose are performed to prepare a polyaniline (PANI)/cotton composite. The polymerization is conducted at the cotton interface. The resultant PANI/cotton composite shows chiroptical activity elucidated with diffuse reflectance circular dichroism. In this reaction, textile‐surface interfacial asymmetric polymerization is performed with imprinting of chiral structure from the cotton as a natural chiroptically active polymer to the PANI. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41118.