Colloidal layered double hydroxides (LDH) nanosheets were sorted by their lateral sizes using a density gradient ultracentrifuge separation technique. Composition investigations on these size-sorted nanosheets indicated that larger sheets had higher Mg:Al ratio than the smaller ones. Experiments using different Mg:Al feed ratios confirmed that high Mg:Al ratio induced fast sheet growth speed. Tracking the source of the Mg:Al spatial distribution difference in one batch of synthesis at the nucleation process revealed the coprecipitation-redissolution of Mg(2+). Thus the discriminative separation of these nanosheets led to a new insight into the structure-composition relationship of LDH nanomaterials and more understanding on their formation mechanism.