ABSTRACT Recently, great efforts have been made to gain highly conductive fabrics for smart textiles and flexible electromagnetic shielding materials. Different from the conventional chemical synthesis method, fibrillar polypyrrole was synthesized on the cotton fabrics via a simple chemical polymerization process with micelles of cationic surfactant (cetyltrimethylammonium bromide, CTAB) as soft template. The modified cotton fabric exhibited excellent electrical conductivity and electromagnetic interference shielding effectiveness due to the formation of fibrillar polypyrrole on the fiber surface. Electrical conductivity of fabric surface were studied by four‐probe resistivity system. The highly conductive fabric with surface conductivity of 5.8 S cm−1 could be obtained by changing cationic surfactant concentration. The electromagnetic interference shielding effectiveness (EMI SE) of the modified fabrics was evaluated by the vector network analyzer instrument. Compared with the sample without using surfactant, the EMI SE value of PPy‐coated cotton fabrics increased by 28% after using 0.03 M CTAB as soft template. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43601.