Here, we demonstrate the fabrication of reduced graphene oxide films on different carbon-based substrates including glassy carbon electrodes (GCEs), graphite electrodes, and carbon paste electrodes through a green approach via a direct electro-deposition technique. The resulting electrochemically reduced graphene oxide (ERGO) films have been investigated by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The as-prepared ERGO film modified electrodes show different and significant electrocatalytic activity toward nitrite oxidation. Among them, the ERGO film modified GCE (ERGO/GCE) has been proven to function as electron transfer mediator and possess high electrocatalytic activity, stability and sensitivity, which might be attributed to the unique structural features of ERGO/GCE.