The present invention relates to an apparatus and method of preparing carbonate and/or formate from carbon dioxide. The apparatus of preparing carbonate and/or formate from carbon dioxide (CO2), comprising: an electrolysis reactor comprising (i) an anode which contains an aqueous solution of a Group I metal salt as an electrolytic solution, (ii) an ion-exchange membrane through which metal cations derived from the Group I metal salt and water flow from an anode to a cathode, (iii) a cathode, and (iv) a gas diffusion layer which supplies a carbon dioxide-containing gas to the cathode; a power supply unit of applying a voltage between the anode and the cathode; a first gas-liquid separator of recovering the electrolytic solution from the products formed in the anode; a second gas-liquid separator of recovering carbonate and/or formate from the products formed in the cathode; a pH meter of measuring the pH of the electrolytic solution recovered from the first gas-liquid separator; a first reactant supply unit of supplying (a) the electrolytic solution recovered from the first gas-liquid separator and (b) the aqueous solution of the Group I metal salt with which the recovered electrolytic solution is replenished according to the pH of the electrolytic solution, to the anode; and a second reactant supply unit of supplying carbon dioxide or a mixer comprising carbon dioxide and water vapor to the cathode; wherein, when a voltage is applied between the anode and the cathode, in the anode, water undergoes electrolysis to generate hydrogen ions, oxygen, and electrons, and metal cations in the Group I metal salt are substituted with the hydrogen ions, while the generated metal cations move to the cathode through the ion-exchange membrane and the electrons move to the cathode through an external electric line; and in the cathode, carbon dioxide, water, metal cations, and electrons are reacted and produce carbonate and/or formate.