The utility model provides an electrode assembly, and an electrochemical device employing the electrode assembly. The electrode assembly comprises a plurality of unit batteries, wherein each unit battery adopts an all-battery or dual-battery structure which comprises an anode, a cathode, and a first diagram arranged between the anode and the cathode; the unit batteries are surrounded by second diagrams, so as to be stacked; the average pore diameter (d2) of the second diagrams is larger than the average pore diameter (d1) of the first diagrams in the unit batteries. The electrode assembly provided by the utility model achieves higher wettability, as well as better performance in removing a gas generated from side reaction of the batteries, so that electrolyte leakage is avoided, battery expansion is reduced, and the electrode assembly finally maintains good battery performance even after long-term use and achieves smaller deformation after external impact.