Mechanical alloying (MA) was carried out to investigate the MA behaviour of the immiscible Al-10, 30 at % Bi alloys. After the MA processing, the Al and Bi were finely and homogeneously alloyed. The Bi crystallite size decreased to 25 nm and 30 nm in the Al-10 at % Bi and Al-30 at % Bi alloys, respectively. By increasing the MA time, the hardness increased up to a value of 80 H-v, which is larger than that obtained from the rule of mixtures. The lattice parameter of Bi decreased by about 0.27%, which shows the formation of a non-equilibrium hcp Bi super-saturated solid solution. The extended solubility of Al in Bi was 1.9% in the Al-30 at % Bi alloy. Due to the extended solubility, depression of the melting temperature of hcp Bi was confirmed in the mechanically alloyed Al-Bi alloys. The maximum depression in the temperature was about 10 K. The measured values corresponded well with those estimated from the extrapolation of the solidus line.