In this paper, Pb-63%Sn alloy was selected as an intermediate layer to plate on Q235 steel by the hot dipping method, and then the hot-dipped steel and the lead plate were welded by roll-bonding technology to prepare the lead-steel layered composite electrode materials. Scanning electron microscopy (SEM), Energy dispersion spectrum (EDS) and X-ray diffraction (XRD) were used to characterize the interface morphology and phase composition of samples, and the interface formation mechanism was also discussed. The electrochemical properties of the lead-steel layered composite electrode under different rolling reduction ratio were studied by linear sweep voltammetry (LSV), Tafel polarization curves (Tafel) and weight-loss method. Subsequently, the prepared lead-steel layered composite electrodes were applied to the industrial production experiment for adiponitrile. The results indicated that lead-steel layered composite electrodes with excellent electrochemical properties were successfully prepared by hot dipping and roll-bonding technology. Analysis of microstructure and phase composition showed that the metallurgical bond of hot-dipped steel and lead plate could be achieved by the process of rolling, and the fracture feature was ductile fracture. And the conductivity, electrocatalytic activity and corrosion resistant of lead-steel layered composite electrode material were improved with the increase of rolling reduction ratio. The industrial production results showed that, compared with the traditional Pb-0.6%Ag electrode, the prepared lead-steel layered composite electrode at the rolling reduction ratio of 40% exhibited the best industrial performance, the current efficiency was increased by 4.94%, the average cell voltage was reduced by 19.4%, and the adiponectin yield was increased by 4.86%.