We investigate energy transfer and electron transfer in a dimethylsilylene-spaced aminostyrene-stilbene donor-acceptor dimer using time-dependent density functional theory calculations. Our results confirm that the vertical S3, S2, and S1 excited states are, respectively, a local excitation on the aminostyrene, local excitation on the stilbene, and the charge-transferred (CT) excited state with electron transfer from aminostyrene to stilbene. In addition, an energy minimum with the C-N bond of the amino group twisted at about 90° is also identified on the S1 potential energy surface. This S1 state exhibits a twisted intramolecular charge transfer (TICT) character. A potential energy scan along the C-N bond torsional angle reveals a conical intersection between the S2 stilbene local excitation and the S1 CT/TICT state at a torsional angle of ∼60°. We thus propose that the conical intersection dominates the electron transfer dynamics in the donor-acceptor dimer and copolymers alike, and the energy barrier along the C-N bond rotation controls the efficiency of such a process. Moreover, we show that despite the zero oscillator strength of the S1 excited states in the CT and TICT minima, an emissive S1 state with a V-shaped conformational structure can be located. The energy of this V-shape CT structure is thermally accessible; therefore, it is expected to be responsible for the CT emission band of the dimer observed in polar solvents. Our data provide a clear explanation of the complex solvent-dependent dual emission and photoinduced electron transfer properties observed experimentally in the dimer and copolymer systems. More importantly, the identifications of the conical intersection and energy barrier along the C-N bond rotation provide a novel synthetic route for controlling emissive properties and electron transfer dynamics in similar systems, which might be useful in the design of novel organic optoelectronic materials.