A novel microsensor to Hg2+ was fabricated through self-assembly of aqueous CdTe nanoparticles (NPs). The morphologies of self-assembly mainly included classical dendrites, straight dendrites, and small islands. The formation process of these morphologies was systematically investigated by using the field emission scanning electron microscope, confocal laser scanning microscope, and atom force microscope instruments, etc. The proposed mechanism showed that the dendrite structure was formed via manipulating the short-range van der Waals interaction and long-range electrostatic interaction, which was realized through altering the ligand and concentration of the CdTe NPs. Furthermore, polymers with positive charges were used to effectively control the morphology of the self-assembly as well as improve the property of photoluminescence. These CdTe dendrites were used as microsensors to Hg2+, which presented the advantages of low cost, quick detection time, high selectivity, and easy operation.