In this study, the effect of alcohols as solvents on the kinetics and the tacticity of poly(N-Isopropylacrylamide) (PNIPAM) is investigated with a combined static and molecular dynamics set of computational tools. Classical molecular dynamics calculations have been carried out to determine the location of the solvent molecules in the proximity of the monomer and the dimer. A combined implicit/explicit solvent model was used for the evaluation of the kinetics of the dimeric polymer chains. Rate constants are calculated with the B3LYP/6-311 + G(d,p)//B3LYP/6-31 + G(d), BMK/6-311 + G(d,p)//B3LYP/6-31 + G(d), and MPWB1K/6-311 + G(d,p)//B3LYP/6-31 + G(d) methodologies via the standard transition state theory. We show that due to the proximity of the –NH and carbonyl groups on the syndiotactic propagating dimeric and trimeric chains, the alcohol can stabilize the corresponding transition states by forming a bridge between these functionalities and accelerate this path more than its isotactic counterpart. In agreement with experiment, the increase in the syndiotactic PNIPAM and the acceleration of the reaction in the presence of t-BuOH is predicted with all the DFT functionals utilized in this study.