Sodium rhodizonate (Na2C6O6) has very high theoretical capacity as a positive electrode material of sodium-ion batteries, but it still has problems such as low actual capacity and poor electronic/ionic conductivity. In order to improve its conductivity, we investigated its structure and electrical properties under high pressure. By performing in situ X-ray diffraction, Raman, infrared absorption, and alternating current impedance spectroscopy in the range of 0-30 GPa at room temperature, we observed a phase transition at ∼11 GPa, with the conductivity increasing by an order of magnitude. Above ∼20 GPa, Na2C6O6 gradually amorphized. During the decompression process, the pressure regulation of the structure and properties of the material are reversible. Our study shows that applying external pressure is an effective tool to improve the conductivity of molecular battery materials. The investigation will help to obtain next-generation electrode materials.