The electrochemical synthesis of silver nanoparticles (nano-Ag) has been successfully carried out on glassy carbon electrode (GCE) and indium tin oxide electrode (ITO) using 1-butyl-3-methylimidazolium tetrafluoroborate (BMT) as green electrolytes. Further the electrodeposited nano-Ag modified ITO electrode has been examined using atomic force microscopy (AFM), and X-ray diffraction studies (XRD). The electrodeposited Ag nanoparticles on ITO were found in the size range of 5 to 3561nm. The nano-Ag film modified GCE was further coated with nafion (Nf) and BMT (165:651 ratio) mixture and found to be stable in BMT and in pH617 phosphate buffer solution (PBS). The nano-Ag/BMT-Nf film modified GCE successfully applied for the oxygen reduction reaction in neutral pH (pH617.0 PBS). The proposed film modified GCE successfully reduces the over potential and show well defined reduction peaks for the detection of dissolved oxygen using cyclic voltammetry (CV) and rotating disc voltammetry (RDE). The film also applied for the detection of dissolved oxygen using electrochemical impedance spectroscopic studies (EIS).