We present calculated one- and two-photon absorption (OPA, TPA) spectra for molecular neutral, cation, and anion cadmium chalcogenide nonstoichiometric clusters [CdnE'(m')(ER)(m), E = S and Se, R = hydrogen, methyl, phenyl, para-nitrophenyl, para-cyanophenyl], ranging from less than 1 nm to more than 2 nm in size with well-defined structures. A systematic treatment of the clusters is carried out to assess the effects of size and ligand on their linear and nonlinear optical properties. Ligands and cluster size were found to have a large influence on the color and intensity of the electronic absorption spectra. TPA cross sections were found to increase linearly with cluster size. Electron-accepting ligands were also found to induce linear enhancement in TPA cross sections. Blue shifts of TPA maxima were observed for the first band with reduced molecular size. The effects of phenyl, para-nitrophenyl, and para-cyanophenyl substitutions, as well as changes in the chalcogenide atom, have been analyzed in detail.