A coupled Cellular Automaton (CA)–Finite Element (FE) model is presented for the prediction of solidification grain structures coupled with the calculation of solid and liquid flow induced macrosegregation. The model is applied to simulate the solidification of a Pb–48wt%Sn alloy in a rectangular cavity cooled down from only one of its vertical boundaries. The algorithm and the numerical implementation of the coupling between the CA and FE methods are first validated by considering a single grain developing with no undercooling. Such a CAFE simulation is shown to retrieve the solution of a purely FE method simulation for which the grain structure is not accounted for. Several applications of the model are then presented to quantify the effects of the grain structure on the final macrosegregation map. In particular, the effect of the undercooling of the columnar front, the presence of equiaxed grains nucleated in the undercooled liquid, as well as the transport and sedimentation of equiaxed grains are investigated. Although good validation is reached when comparing computed and measured segregation profiles available in the literature for the chosen configuration, it is concluded that refined experimental data are required to further validate the predictions of a coupled CAFE model.