In this article, we demonstrated by the application of time-resolved spectroscopy, X-ray structural analysis and other spectroscopic techniques that 9-Anthrylsilanes exhibits sigma,pi*-interaction between 9-anthryl group and the Si-Si linkage in anthryl-disilanes, ASi(2), ASi(2)A, and ASi(3)A which does not occur in the analogous alkyl derivatives as well as the pyrenylsilane, derivatives, in spite of the fact that the 0,0-band of PSi2 is about 12.8 KJ more energetic than that of ASi(2) (Figure 1). More interestingly, the X-ray structural studies reveal that ASi(3)A exists in a butterfly-like structure in agree-ment with other spectroscopic analyses that the two anthryl groups do not interact in their excited states, while those in ASi(2)A do. This is in contrast to the analogous pyrenylsilanes; the trisilanes exhibits a stronger excimer interaction than that of disilane.(10b) Our results show that the sigma,pi*-interactions in ASi(3)A has imparted rigidity to the tri-silyl linkage. Potential applications of anthrylsilanes in material sciences will be explored.(5) This work provides evidence that sigma,pi*interaction between the 9-anthryl group and disilyl linkage does play an important role in the properties of disilanes. We attribute this enhanced sigma,pi*-interaction to the nature of the lowest excited state (S-1 state) of anthracenes, the La transition, which has a much higher oscillator strength than the S1Lb-transition of pyrenes (Figure 1). We define the interaction in anthracene as a sigma,pi*(S1La) interaction. This interaction lends a substantial barrier to the Si-Si bond with the excited anthryl nucleus in anthrylsilanes. The scope and potential applications of this phenomenon are discussed.