Based on solidification theory and a volume-averaged multiphase solidification model, the solidification process of NH4Cl-70 pct H2O was numerically simulated and experimentally verified. Although researchers have investigated the solidification process of NH4Cl-70 pct H2O, most existing studies have been focused on analysis of a single phenomenon, such as the formation of channel segregation, convection types, and the formation of grains. Based on prior studies, by combining numerical simulation and experimental investigation, all phenomena of the entire computational domain of the solidification process of an NH4Cl aqueous solution were comprehensively investigated for the first time in this study. In particular, the sedimentation of equiaxed grains in the ingot and the induced convection were reproduced. In addition, the formation mechanism of segregation was studied in depth. The calculation demonstrated that the equiaxed grains settled from the wall of the mold and gradually aggregated at the bottom of the mold; when the volume fraction reached a critical value, the columnar grains stopped growing, thus completing the columnar-to-equiaxed transition (CET). Because of solute partitioning, negative segregation occurred at the bottom region of the ingot concentrated with grains, whereas a wide range of positive segregation occurred in the unsolidified, upper part of the ingot. Experimental investigation indicated that the predicted results of the sedimentation of the equiaxed grains in the ingot and the convection types agreed well with the experimental results, thus revealing that the sedimentation of solid phase and convection in the solidification process are the key factors responsible for macrosegregation.