A novel, single step preparation of copper nanoparticles decorated silver nanoleaves (AgNLs–CuNPs) bimetallic composite at glassy carbon electrode (GCE) was done through electrochemical potentiostatic method. Three different morphologies namely, nanoparticles, nanodentrites and nanoparticles decorated nanoleaves were obtained for copper, silver and silver–copper as the result of deposition. Moreover, the obtained AgNLs–CuNPs composite is highly dense compared to their individuals. This was confirmed by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The crystal planes and elemental composition of the prepared nanocomposites were examined by X-ray diffraction (XRD) spectroscopy, Energy dispersive X-ray (EDX) spectroscopy and X-ray photoelectron spectroscopy (XPS). The highly dense AgNLs–CuNPs composite modified GCE showed a well-defined cathodic peak at −0.195V towards H2O2. The cyclic voltammetry and amperometric studies revealed the excellent electrocatalytic ability of AgNLs–CuNPs/GCE towards the reduction of H2O2 compared to only AgNDs and CuNPs. Remarkably, the fabricated AgNLs–CuNPs/GCE displayed a very low detection limit (0.095μM) with high sensitivity (6190μAmM−1cm−2). Our demonstrated sensor holds good in a linear range from 0.5 to 1015μM. Additionally, the selective determination of hydrogen peroxide was achieved using AgNLs–CuNPs/GCE even in the presence of other interfering biomolecules. The real sample analysis was performed in commercial clinical lens cleaning solutions to demonstrate the practicability of our sensor.