In the present study, the electrochemiluminescence application of the fabricated Ni-foam electrode with copper oxide nanostructures to determine hydrogen peroxide was presented for the first time. Copper oxide nanostructures were anchored on the Ni-foam surface by silica template as the morphology-adjusting factor. The proposed electrode has a three-dimensional surface and an acceptable electrocatalytic feature to the hydrogen peroxide–luminol system at the negative potential as − 0.18 V vs. Ag/AgCl. Electrochemical impedance spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, and X-ray photoelectron spectroscopy were utilized for consideration of the conductivity and surface morphology of the fabricated electrode. The fabricated electrode was utilized as an ECL sensor to monitor hydrogen peroxide with a logarithmic response in a wide linear range of 2.9 × 10–13 to 2.7 × 10–8 M and a low detection limit of 3.0 × 10–14 M (S/N = 3). Also, good repeatability and long-term stability were gained for the fabricated electrode. Owing to the superior properties of the developed ECL sensor, this method as a new probe was fulfilled for the monitoring of hydrogen peroxide in the milk sample.