Surface functionalization of carbon nanotubes (CNTs) by biological adhesive polymers carbopol (CP) was developed by simply mixing CNT suspension and an aqueous solution of CP without any toxic solvents. CP can be easily coated onto CNTs through hydrogen bonds OCOH⋯NH2CO and electrostatic interaction between COO on CP and NH3+ on CNTs. After modification, the surface of the CNT is endowed with a large number of carboxyl groups, which can effectively prevent the reaggregation of CNT by electrostatic repulsion between the ionized carboxyl groups. Hence, highly dispersed functionally modifying CNT by CP (CP‐CNT) filler in polydimethylsiloxane (PDMS) matrix can be obtained. More important, with the help of adhesive properties of CP, the interfacial compatibility between fillers and matrix can also be improved. Thus, the CP‐CNT/PDMS composites exhibited higher dielectric permittivity comparing with CNT/PDMS composites at the same filler content. We present a potential and green approach of surface functionalization of CNT for preparing high‐permittivity polymer composites. J. VINYL ADDIT. TECHNOL., 26:165–172, 2020. © 2019 Society of Plastics Engineers