This study reports the structural evolution of equiatomic AlCuNiFeTi high-entropy alloy (HEA) from elemental materials to solid solution during mechanical alloying (MA), and further, to equilibrium phases during subsequent thermal annealing. It was justified experimentally that MA of Al-Cu-Ni-Fe-Ti powder mixture during 15 hours resulted in a single-phase nanocrystalline HEA with a structure of ВCC solid solution. During thermal annealing recovery and recrystallization of the BCC solid solution take place at temperatures ranging from 130 to 650 °C, and phase transformation, and grain growth of equilibrium phases occur at higher temperatures. The phase composition transforms to BCC and FCC solid solutions when the MA powder was annealed at 700 °C for 1 h. The BCC and FCC solid solution structure can be maintained even after the alloy was annealed at 1000 °C. The alloy powder was consolidated by pressure sintering at 800 °C with 5 GPa pressure for half an hour. The sintered sample exhibits 10.7±0.3 GPa in Vickers hardness.