HfO2/SiO2 multilayer films were deposited on BK7 glass substrates by electron beam evaporation method. The effects of annealing at the temperature between 200 and 400 centigrade on residual stresses have been studied. It is found that the residual stress of as-deposited HfO2/SiO2 multilayers is compressive. It becomes tensile after annealing at 200 centigrade, and then the value of tensile stress increases as annealing temperature increases. And cracks appear in the film because tensile stress is too large when the sample is annealed at 400 centigrade. At the same time, the crystallite size increases and interplanar distance decreases with the increase of annealing temperature. The variation of residual stresses is corresponding with the evolution of structures.