The effects of hydration on vibrational normal modes of trimethylamine N-oxide (TMAO) are investigated by Raman spectroscopy and electronic structure computations. Microsolvated networks of water are observed to induce either red or blue shifts in the normal modes of TMAO with increasing water concentration and to also exhibit distinct spectral signatures. By taking advantage of the selective and gradual nature of the water-induced shifts and using comparisons to theoretical predictions, the assignments of TMAO's normal modes are re-examined and the structure of the hydrogen-bonded network in the vicinity of TMAO is elucidated. Agreement between experiment and theory suggests that the oxygen atom in TMAO accepts on average at least three hydrogen bonds from neighboring water molecules and that water molecules are likely not directly interacting with TMAO's methyl groups.