A comprehensive Raman spectroscopic/electronic structure study of hydrogen bonding by pyrimidine with eight different polar solvents is presented. Raman spectra of binary mixtures of pyrimidine with methanol and ethylene glycol are reported, and shifts in v(1), v(3), v(6a), v(6b), v(8a), v(8b), v(9a), v(15), v(16a), and v(16b) are compared to earlier results obtained for water. Large shifts to higher vibrational energy, often referred to as blue shifts, are observed for v(1), v(6b), and v(8b) (by as much as 14 cm(-1)). While gradual blue shifts with increasing hydrogen bond donor concentration are observed for v(6b) and v(8b), v(1) exhibits three distinct spectral components whose relative intensities vary with concentration. The blue shift of v(1) is further examined in binary mixtures of pyrimidine with acetic acid, thioglycol, phenylmethanol, hexylamine, and acetonitrile. Electronic structure computations for more than 100 microsolvated structures reveal a significant dependence of the magnitude of the v(1) blue shift on the local microsolvation geometry. Results from natural bond orbital (NBO) calculations also reveal a strong correlation between charge transfer and blue shifting of pyrimidines normal modes. Although charge transfer has previously been linked to blue shifting of the X-H stretching frequency in hydrogen bond donors, here, a similar trend in a hydrogen bond acceptor is demonstrated.