The pi-pi and sigma-pi interactions in alpha,omega -di-1-naphthyl and di-9-anthryl oligosilanes [Np-(SiMe2)(n)-Np (1-4), Ant-(SiMe2)(n)-Ant (5-8), n = 1-4] were investigated in solution. In nonpolar solvents such as cyclohexane, a strong excimer fluorescence is observed, which indicates a strong pi-pi interaction. In a polar solvent (CH3CN), a charge-transfer (CT) emission is observed for 3 and 4 due to the sigma-pi interaction.