A novel strategy of designing high-performance non-equimolar HEAs was proposed.
Lower Al and higher (Cr, Ni) lead to higher level of compositional segregation.
Al plays a vital role in phase formation of alloys in AlCrFeCoNi HEA system.
Cr and Ni could modify the mechanical properties of HEAs in AlCrFeCoNi HEA system.
Lamella-like and dendrite structures exhibit high mechanical properties.