Abstract Ni(OH) 2 nanoflowers were synthesized by a simple and energy‐efficient wet chemistry method. The product was characterized by scanning electron microscopy (SEM) and X‐ray powder diffraction (XRD). Then Ni(OH) 2 nanoflowers attached multi‐walled carbon nanotubes (MWCNTs) modified glassy carbon electrodes (GCE) were proposed (MWCNTs/Ni(OH) 2 /GCE) to use as electrochemical sensor to detect hydrogen peroxide. The results showed that the synergistic effect was obtained on the MWCNTs/Ni(OH) 2 /GCE whose sensitivity was better than that of Ni(OH) 2 /GCE. The linear range is from 0.2 to 22 mmol/L, the detection limit is 0.066 mmol/L, and the response time is <5 s. Satisfyingly, the MWCNTs/Ni(OH) 2 /GCE was not only successfully employed to eliminate the interferences from uric acid (UA), acid ascorbic (AA), dopamine (DA), glucose (GO) but also NO 2 − during the detection. The MWCNTs/Ni(OH) 2 /GCE allows highly sensitive, excellently selective and fast amperometric sensing of hydrogen peroxide and thus is promising for the future development of hydrogen peroxide sensors.