Several aspects of the photoinduced electron transfer (ET) reaction between coumarin 314 (C314) and N,N-dimethylaniline (DMA) at the water/DMA interface are investigated by molecular dynamics simulations. New DMA and water/ DMA potential energy surfaces are developed and used to characterize the neat water/DMA interface. The adsorption free energy, the rotational dynamics, and the solvation dynamics of C314 at the liquid/liquid interface are investigated and are generally in reasonable agreement with available experimental data. The solvent-free energy curves for the ET reaction between excited C314 and DMA molecules are calculated and compared with those calculated for a simple point charge model of the solute. It is found that the reorganization free energy is very small when the full molecular description of the solute is taken into account. An estimate of the ET rate constant is in reasonable agreement with experiment. Our calculations suggest that the polarity of the surface "reported" by the solute, as reflected by solvation dynamics and the reorganization free energy, is strongly solute-dependent.