Graphene is extremely sensitive to its surrounding environment. In fact, any modification on its surface, such as an adsorption of a molecule, can change its properties. The conductivity of graphene is a crucial parameter to be examined for potential graphene-based applications, especially biosensors. In this paper, we have investigated the effects of non-covalent functionalization based on π–π interaction, using 1-pyrenebutyric acid N-hydroxysuccinimide ester (PBASE), on the conductivity of graphene-based electrodes by electrochemical techniques. Graphene layers were obtained by chemical vapor deposition (CVD) and characterized by Raman spectroscopy, Scanning Electron Microscopy (SEM), and X-Ray Diffraction (XRD). The results demonstrate the synthesis of a high quality and continuous monolayer graphene with an I_2D/I_G ratio = 2.71 and I_D = 0. After the functionalization of graphene-based electrode with PBASE, the electrochemical analyses confirmed a p-doping effect existence influencing the conductivity by increasing the charge transfer resistance R_ct from 816.5 to 2213 Ω. Furthermore, increasing the concentration of PBASE from 5 mM to 10 mM did not affect the conductivity as the R_ct did not change. Solvent adsorption was found to be the main cause of the decrease in conductivity during the functionalization process. This study highlights the effect of non-covalent π-π stacking of PBASE on graphene to tune the electrical properties of graphene through functionalization processes for a better performance for their use as biosensors. Graphical abstract: (Figure presented.).