Nanosized single and multiple layers of electroless Ni films were deposited on Fe film. The multilayer films consisting of a Fe/(Ni1 Ni2)n structure, where Ni1 and Ni2 denote various electroless Ni films deposited in plating baths with different pH values, and n denotes layer numbers and equals to 2, 4, 8, and 16, were formed by alternately changing the pH value of plating baths under controlled deposition time during the deposition process. The ensuing results showed that the boundaries between films are almost even. The deposition of various electroless Ni films on Fe film can increase the coercivity and squareness ratio of Fe film.