Two electron oxygen reduction reaction to produce hydrogen peroxide (H2O2) is a promising alternative technique to the multistep and high energy consumption anthraquinone process. Herein, Ni–Fe layered double hydroxide (NiFe-LDH) has been firstly demonstrated as an efficient bifunctional catalyst to prepare H2O2 by electrochemical oxygen reduction (2e− ORR) and oxygen evolution reaction (OER). Significantly, the NiFe-LDH catalyst possesses a high faraday efficiency of 88.75% for H2O2 preparation in alkaline media. Moreover, the NiFe-LDH catalyst exhibits excellent OER electrocatalytic property with small overpotential of 210 mV at 10 mA cm−2 and high stability in 1 M KOH solution. On this basis, a new reactor has been designed to electrolyze oxygen and generate hydrogen peroxide. Under the ultra-low cell voltage of 1 V, the H2O2 yield reaches to 47.62 mmol gcat−1 h−1. In order to evaluate the application potential of the bifunctional NiFe-LDH catalyst for H2O2 preparation, a 1.5 V dry battery has been used as the power supply, and the output of H2O2 reaches to 83.90 mmol gcat−1 h−1. The excellent electrocatalytic properties of 2e− ORR and OER make NiFe-LDH a promising bifunctional electrocatalyst for future commercialization. Moreover, the well-designed 2e− ORR-OER reactor provides a new strategy for portable production of H2O2.