Linear and nonlinear optical properties of three families of inorganic clusters (n-Bu(4)N)(3)[MS(4)M’(3)XX’(3)], MS(4)M’(3)X(PPh(3))(3), and (n-Bu(4)N(2))(2)[MOS(3)M’(3)X’(3)] (M = Mo, W; M’ = Cu, Ag; X = Cl, Br; X’ = Cl, Br, I, SCN) were compared. Synthetic routes leading to these clusters are discussed along with the structural and compositional aspects that influence clusters’ optical performance. A scheme to understand these influences is proposed based on qualitative molecular orbital considerations.