The solidification of Al-4.6Cu-0.5Fe-0.5Mn (206 type) cast alloy has been studied using Thermal Analysis, Differential Scanning Calorimeter, Scanning Electron Microscopy, Electron Back-Scattered Diffraction (EBSD), and Transmission Electron Microscopy (TEM). It is interesting to note that an iron-rich intermetallic phase, Al-3(FeMn), is experimentally observed to be dominantly present in the fully solidified cast structure of the experimental 206 cast alloy, in addition to beta-Fe (Al7Cu2(FeMn)/Al7Cu2Fe) phase. Al-3(FeMn) phase is formed through a eutectic reaction approximately at 640 degrees C during solidification, possibly resulting from the phase selection and segregation of Fe in liquid Al. The presence of the Al-3(FeMn) phase has been confirmed by both EBSD and TEM. It is also found that both beta-Fe and Al6(FeMn) are possible to nucleate on Al-3(FeMn), as confirmed by the calculated low planar disregistries. The possible solidification reactions have been established for 206-type cast alloy at 0.5% Fe.