A novel and easy fabrication of MPS-nano Ag/nafion (NF) film modified sensor has been constructed based on the self adsorption of 3-mercapto-1-propane sulfonic acid (MPS) over a pretreated glassy carbon electrode (GCE) followed by the electrochemical depositions of Ag nano particles (nano Ag) with manual nafion coating (5 μL). Further the MPS-nano Ag/NF film modified semiconductor indium tin oxide electrodes (ITO) were examined by using SEM and AFM techniques. From these analyses, it was found that the nano Ag particles were uniformly deposited on the MPS layer and the sizes were in the range of 20 to 70 nm. Further the nano Ag/NF film deposited onto the self adsorbed surface of MPS exhibits excellent electrocatalytic activity for the oxygen reduction reaction (ORR) at a reduced potential (-0.4 V). Proposed MPS-nano Ag/NF film modified GCE is easy to fabricate and has the advantage of good stability, reproducibility, and shows rapid response for oxygen reduction, respectively.