Ground-state configurations of bromomethane molecules under external electric fields were optimized on B3LYP/6-311G++(d, p) basis set using density functional theory. Molecular structure, total energy, dipole moment, bond length, charge distribution, orbital energy level, infrared spectroscopy, Raman spectroscopy and dissociation potential energy curve were analyzed computationally. It shows that with the increase of external electric field (0 a.u. -0.02 a.u.) along Y axis (parallel to the 1C-4Br line), the total molecular energy decreases, the 1C-4Br bond length increases, and the molecular dipole moment increases, the molecular energy gap decreases gradually, and the molecular infrared spectrum exhibits a blue shift. The dissociation potential energy curve shows that an external electric field with a strength of 0.02 a.u. makes the 1C-4Br bond broken and the molecule degraded.