Raman multivariate curve resolution (Raman-MCR) is applied to examine how the hydration shell around poly(N,N-diethylacrylamide) (PDEAM) changes upon heating, in comparison with poly(N-isopropylacrylamide) (PNIPAM), both of which undergo a clouding transition near room temperature. We report that PDEAM possesses a less-ordered and smaller hydration shell than PNIPAM. Furthermore, the PDEAM hydration-shell structure is insensitive to the occurrence of clouding, indicating the coil-globule transition and aggregation of multiple chains can be achieved without the hydration-shell structural transformation.