The equiatomic multicomponent CoCrFeNiCuAl high-entropy alloy powder was synthesized by mechanical alloying. The effects of milling time and heat treatment on the structure and morphology of the ball milled alloy were investigated. Single BCC solid solution structure appears when the alloy is ball milled more than 30h. The 60h ball milled alloy powder shows a mean particle size of 3 μm, which is actually hard agglomerations of nanosized crystals with crystalline size less than 10nm. The 60h ball milled alloy exhibits good chemical homogeneity. The single BCC solid solution structure transforms to a BCC and a FCC phases when annealled at 600°C for 1h, which can be attributed to the supersaturatable solid solution formation during the mechanical alloying process.