In this work, we carried out a systematic investigation to assess the effects of ligands on the structure, stability, and absorption spectra of ultrasmall CdSe tetrahedral quantum dots, where the cores of small tetrahedral quantum dots have been postulated to be stabilized by amine and carboxylate ligands. We found that amine and carboxylate ligands form extensive hydrogen bonding networks, which provide thermodynamic stability to the clusters. On the basis of the optimized structures, good agreement between observed and computed spectra was obtained. The ligands were also found to have a large influence on the color and intensity of the electronic absorption spectra, particularly for the small clusters, which were previously monitored with in situ UV-visible absorbance spectroscopy. Our work provides an understanding of the effect of ligands that influence thermodynamic stability and electronic absorption of ultrasmall quantum dots, thus potentially motivating further experimental exploration.