This work reports on the fabrication and comparative analytical assessment of electrochemical sensors applied to the rapid analysis of chemical oxygen demand (COD) in urban waste waters. These devices incorporate a carbon nanotube-polystyrene composite, containing different inorganic electrocatalysts, namely, Ni, NiCu alloy, CoO, and CuO/AgO nanoparticles. The sensor responses were initially evaluated using glucose as standard analyte and then by analyzing a set of real samples from urban wastewater treatment plants. The estimated COD values in the samples were compared with those provided by an accredited laboratory using the standard dichromate method. The sensor prepared with the CuO/AgO-based nanocomposite showed the best analytical performance. The recorded COD values of both the sensor and the standard method were overlapped, considering the 95% confidence intervals. In order to show the feasible application of this approach for the detection of COD online and in continuous mode, the CuO/AgO-based nanocomposite sensor was integrated in a compact flow system and applied to the detection of wastewater samples, showing again a good agreement with the values provided by the dichromate method.