The invention discloses a resistive random access memory (RRAM) with a metamaterial electrode structure and a preparation method of the RRAM. The resistive random access memory comprises a substrate and an electrode-resistive layer-electrode structure arranged on the substrate, wherein the electrode is of a metamaterial structure capable of producing resonance to an electromagnetic field. The method comprises the steps that firstly, a resistive thin-film material layer is grown with a traditional semiconductor CMOS process on the substrate; then, a photoresist is taken as a sacrificial layer, and an electrode pattern with the metamaterial structure is etched on the resistive thin-film material layer with a photolithography of the traditional thin-film material CMOS process via the sacrificial layer; a metal electrode material is deposited on the etched pattern, and the structure of the resistive random access memory is formed after the sacrificial layer is removed. According to the method, the metamaterial is made into the electrode structure and applied to the resistive random access memory, and the change of a storage state is realized through non-contact excitation of an electromagnetic wave, so that the resistive random access memory can be applied to aspects of an electromagnetic switch, electromagnetic wave detection and the like, thus, greatly enriching the application of the resistive random access memory.