A hierarchically structured MnOx-NiCo2O4 monolithic catalyst with rich phase interfaces was designed by a simple, eco-friendly and time-saving in-situ electro-deposition method. The abundance of active oxygen species due to this rich phase interfaces contributed to the excellent benzene combustion performance of MnOx-NiCo2O4-2:2 sample, oxidizing about 90% of benzene (T90) at 198 C under 12000 h 1 gaseous hourly space velocity. This work shed new light on the design of excellent monolithic catalysts, which might pave the way for the industrialization of benzene combustion.