The two-body Coulomb explosion of acetonitrile, CH3CN2+ → CH3-n+ + HnCN+ (n = 0–2), in intense laser fields (0.15 PW/cm2, 70 fs) is studied by the coincidence momentum imaging technique. It is found that the fragment ions for n = 0 are ejected mostly in the direction of the laser polarization vector with ⟨ cos2 θ ⟩ = 0.68, where θ is the angle between the fragment recoil direction and the laser polarization vector, while the angle distribution becomes more isotropic as n increases, i.e., ⟨ cos2 θ ⟩ = 0.49 for n = 1 and ⟨ cos2 θ ⟩ = 0.37 for n = 2. From this characteristic correlation between the anisotropy in the fragment ejection and the hydrogen migration, the Coulomb explosion dynamics competing with the hydrogen atom transfer from the methyl group to the nitrile group is investigated.