Disclosed are a process for separating an electrode for membrane-electrode assemblies of fuel cells from the decal transfer film and an apparatus for separating the electrode. In particular, during the electrode separating process, only an electrode is separated from the decal transfer film on which the electrode is coated, without any damage, by a freezing method for freezing the specimen on the deionized water surface, and thus, wasting the expensive MEA is prevented. Thus, mechanical properties of the pristine electrode can be rapidly quantified in advance, and therefore, long term durability evaluation period during developing MEA having excellent durability is substantially reduced.