Disclosed are a multi-block copolymer, its producing method and an electrolyte membrane using the same. The multi-block copolymer includes a hydrophobic block having a plurality of repeating units represented as chemical formula 1; and a hydrophilic block having a plurality of repeating units represented as chemical formula 2. The multi-block copolymer is acidified, and can be used to an electrolyte membrane and a fuel cell. The use of the multi-block copolymer as an electrolyte membrane ensures excellent dimensional stability.