Bimolecular nucleophilic substitution (S(N)2) reactions are of great importance in chemistry and biochemistry due to their capability of constructing functional groups. In this work, we investigate the solvent effect on the free energy profiles of symmetric and asymmetric S(N)2 reactions in the acetonitrile solution using the proposed reaction density functional theory (RxDFT) method. This multiscale method utilizes quantum density functional theory for calculating intrinsic reaction free energy coupled with classical density functional theory for addressing solvation contribution. We find that the presence of acetonitrile brings both the polarization effect and solvation effect on the reaction pathways. For the eight selected symmetric S(N)2 reactions, the predicated reaction pathways agree well with the results from the direct and thermodynamic cycle (TC) methods with the SMD-M062X solvation model. In addition, the polarization effect reduces the free energy barriers by about 6 kcal/mol, while the solvation effect increases the barriers by about 18 kcal/mol. For the four selected asymmetric S(N)2 reactions, the predicted reaction pathways agree well with the results from the Monte Carlo simulations and experiments. The polarization effect and the solvation effect mutually reduce the free energy barriers, and the solvation effect plays a dominant role.