The electrochemical behavior of seven substituted cyclic polysilanes, namely hexamesitylcyclotrisilane (Mes(2)Si)(3) (I), 1,2,3,4-tetra-tert-butyltetramethyl-cyclotetrasilane [t-Bu(Me)Si](4) (II) (mixture of isomers), decapropylcyclopentasilane (Pr2Si)(5) (III), dodecamethylcyclohexasilane (M(e)2Si)(6) (IV), tetradecaethylcycloheptasilane (Et2Si)(7) (V), hexadecamethylcyclooctasilane (Me2Si)8 (VI) and octadecamethylcyclononasilane (Me2Si)(9) (VII), have been studied by cyclic voltammetry and preparative electrolysis in ＇oxygen-free＇ and ＇water-free＇ solutions of CH2Cl2 + CH3CN + CF3COOH (4:1:1) containing sodium trifluoroacetate as the supporting electrolyte. The products are cyclic compounds with one or two oxygen atoms as well as silicon atoms in the rings. The effects of ring size and nature of substituent on the oxidation peak potentials and reactivity of starting materials, and on the selectivity of the outcoming products, are discussed.