Marginal-restraint mandrel-free spinning is an advanced technology for manufacturing ellipsoidal heads with large diameter-thickness ratios. Nevertheless, the spinning-induced residual stress, which greatly influences the in-service performance of spun heads, should be removed. In this study, the effects of annealing on the residual-stress relaxation behavior of 5052H32 aluminum alloy spun heads were investigated. It is found that the residual stress first rapidly decreases and then remains steady with the increase in annealing time at the tested annealing temperatures. The relaxation of the residual stress becomes increasingly obvious with the increase in annealing temperature. When the annealing temperature is less than 220 °C, there are no obvious changes in grain size. Moreover, the spinning-induced dislocations are consumed by the static recovery behavior, which decreases the residual stress during annealing. When the annealing temperature is approximately 300 °C, the broken grains transform into equiaxed grains. In addition, static recrystallization and recovery behaviors occur simultaneously to promote the relaxation of the residual stress. Considering the different stress relaxation mechanisms, a model based on the Zener-Wert-Avrami equation was established to predict the residual-stress relaxation behavior. Finally, the optimized annealing temperature and time were approximately 300 °C and 30 min, respectively.