The relationship between the local solvation structures and global thermodynamics, specifically in the case of amphiphilic molecules, is a complex phenomenon and is not yet fully understood. With the prior knowledge that local solvation structures can impose a significant impact on the overall solvation process, we here combine THz spectroscopic analysis with MD simulations to investigate the impact of the altered hydrophobicity and polarity of amphiphilic solute molecules on the local solvation configurations. We use two water soluble alcohols: ethanol (EtOH) and its fluorinated counterpart, 2,2,2-trifluoroethanol (TFE), as model solutes. Our study is aimed to determine the relative abundance of different hydrogen bonded conformers and to establish a correlation between the spectral signatures (as obtained from THz spectroscopic measurements) and microscopic solute-solvent interactions associated with the local solvation structures (as obtained from MD simulations). Finally, we estimate the possible energetic parameters associated with the alcohol solubilization process. We found that while both the alcohols are completely water soluble, they receive a contrasting solvation energy share in terms of entropy and enthalpy. We understand that these findings are not limited to the specific system studied here but can be broadly extrapolated to other amphiphilic aqueous solutions.