Nickel–iron-layered double hydroxide (NiFeLDH) is one of the promising catalysts for the oxygen evolution reaction (OER) in alkaline electrolytes, but its conductivity limits its large-scale application. The focus of current work is to explore low-cost, conductive substrates for large-scale production and combine them with NiFeLDH to improve its conductivity. In this work, purified and activated pyrolytic carbon black (CBp) is combined with NiFeLDH to form an NiFeLDH/A–CBp catalyst for OER. CBp not only improves the conductivity of the catalyst but also greatly reduces the size of NiFeLDH nanosheets to increase the activated surface area. In addition, ascorbic acid (AA) is introduced to enhance the coupling between NiFeLDH and A–CBp, which can be evidenced by the increase of Fe-O-Ni peak intensity in FTIR measurement. Thus, a lower overvoltage of 227 mV and larger active surface area of 43.26 mF·cm−2are achieved in 1 M KOH solution for NiFeLDH/A–CBp. In addition, NiFeLDH/A–CBp shows good catalytic performance and stability as the anode catalyst for water splitting and Zn electrowinning in alkaline electrolytes. In Zn electrowinning with NiFeLDH/A–CBp, the low cell voltage of 2.08 V at 1000 A·m−2results in lower energy consumption of 1.78 kW h/KgZn, which is nearly half of the 3.40 kW h/KgZnof industrial electrowinning. This work demonstrates the new application of high-value-added CBp in hydrogen production from electrolytic water and zinc hydrometallurgy to realize the recycling of waste carbon resources and reduce the consumption of fossil resources.