Constructed wetlands-microbial fuel cells (CW-MFC) are an innovative technology used for simultaneous bioelectricity generation and wastewater treatment. This is possible due to the installation of macrophytes in an electrode configuration, in which electroactive microorganisms use organic substrates as biofuel. One way to improve the electrochemical performance of CW-MFCs is through the impregnation of cathodic electrocatalysts. Therefore, in this study the bioelectricity production capacity of CW-MFCs was evaluated from the oxygen reduction reaction (ORR). For this study, the concentrations 0 (CW-MFC1), 0.5 (CW-MFC2), and 1 mg/cm2 (CW-MFC3) of graphene/titanium dioxide (G/TiO2) as electrocatalyst on the cathodes were evaluated. Using the Koutecky-Levich analysis, it was determined that the ORR transfer mechanism arises via a 4-electron pathway. The electrokinetic parameters of Tafel slope, charge transfer coefficient, and exchange current density determined the efficiency of the ORR, registering 92 mV/dec, 0.93 (α), and 2.30 x10-3 mA/cm2, respectively for CW-MFC3. The highest electrochemical performance was obtained at a concentration of 1 mg/cm2 (CW-MFC3) of G/TiO2, generating 144 mW/m2 of power density, 157 Ω of internal resistance, −150 mV of anodic potential, and 383 mV of cathodic potential. The surface modification carried out on the cathodes resulted in a catalytic increase in the ORR.