Surface‐confined electropolymerization allowed us to easily prepare homogeneous polymer composite paper structures. The fabrication of freestanding graphene (Gr)‐based composite electrodes is very important for many modular approaches in electrochemical applications, such as fuel cells, supercapacitors, and sensors. A Gr composite paper electrode doped with polymeric films of pyronin Y was fabricated by two repetitive simple applications: vacuum filtration and surface‐confined electropolymerization. The characterization of this composite paper was done with scanning tunneling microscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, powder X‐ray diffraction spectroscopy, Raman spectroscopy, UV–visible absorption spectroscopy, four‐point probe conductivity measurement, cyclic voltammetry, and electrochemical impedance spectroscopy. The freestanding composite paper demonstrated good electrocatalytic activity for the electrooxidation of dopamine; this indicated that this composite paper could be used for the amperometric quantification of dopamine in real samples. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45139.