The equiatomic multiprincipal CoCrFeNiCuAl high-entropy alloy was prepared using a vacuum arc melt casting method. The as-cast alloy was subsequently annealed at 1000 °C for 2 h and the annealing effects on the structure and properties evolution were investigated. The as-cast alloy is composed of simple BCC and FCC solid solutions. The “2” FCC phase precipitates from the ordered BCC matrix and the FCC phases become dominated after the alloy was annealed. Both alloys show typical cast-dendrite morphology and similar elemental segregation. The as-annealed alloy exhibits high strength and excellent ductility of 1.63 GPa and 34%, respectively. Both alloys possess high saturated magnetization and undergo a ferromagnetic transition.