The crystallization of DL-alanine from water/alcohol supersaturated solutions results in the precipitation of a racemic compound displaying a needlelike hollow morphology, in contrast to the needlelike crystals grown from pure aqueous solutions. This unusual morphology is explained by assuming that the supersaturated solutions crystallized rapidly to create DL-alanine nanocrystals that assemble to give mesoscale crystals. The resulting DL-alanine crystals are characterized by a range of techniques such as X-ray diffraction, scanning electron microscopy, micro-Raman, and differential scanning calorimetry. The kinetics was studied by light scattering and ion-solution conductivity. These measurements revealed that these superstructures of DL-alanine mesocrystals consist of three-dimensional DL-alanine nanocrystals. Finally, a mechanism for the formation of DL-alanine mesocrystals with a hollow morphology is proposed.