The structure and decomposition behaviour of rapidly solidified Al-5, 10 and 15 at % Fe alloys have been investigated by detailed transmission electron microscopy and differential scanning calorimetry. Rapid solidification produces a variety of metastable phases : microquasicrystalline, decagonal, Al(m)Fe, Al6Fe and Al13Fe4, in order of increasing thermodynamic stability. The rapidly solidified microstructure depends upon the alloy composition and cooling rate. Primary and cellular particles of the microquasicrystalline phase are preferred at higher cooling rates, and primary or eutectic particles of the Al(m)Fe phase are preferred at lower cooling rates. With increasing iron content, the microquasicrystalline phase is replaced with primary particles of the decagonal phase. After annealing at moderate temperatures, the microquasicrystalline phase in Al-5 and 10 at % Fe decomposes into Al(m)Fe and Al6Fe, and the microquasicrystalline phase in Al-15 at % Fe decomposes into Al(m)Fe. After annealing at higher temperatures, the Al(m)Fe, Al6Fe and decagonal phases then decompose into stable Al13Fe4.