The present paper is devoted to the calculation of transition wavelengths, oscillator strength f, Einstein An0 and B0n coefficients of methyl vinyl siloxane from ground state Cs(X1A′) to the first ten different excited states by employing density functional theory and single substitute configuration interaction approach with basis sets 6-311++G**. At the same time, the excited states of methyl vinyl siloxane under different external electric fields are investigated. It is shown that the HOMO-LUMO gaps become smaller, and the excitation energies of the first ten excited states of methyl vinyl siloxane decrease sharply as the external electric field intensity become strong. The conclusion can be drawn that the transition between the ground state X1A′ and the excited state of methyl vinyl siloxane is easy to bring about.