 highlights RGO-slash-Mzine-slash-TO2-slash-V2C heterointerface porous microspheres prepared via scalable method to boost polarization, customization of hierarchical structure by precisely tuning 2D RGO-slash-Mzine intercalation, optimal reflection loss of minus 67.4 dB and EAB equals 5.47 GHz at low filler loading of 5WT%. Simulations showed the benefits of 2D nanosheets intercalation on polarization loss. This article was authored by Gu Wang, Chongfongli, Diana Estevez, and others.