We present a systematic direct ab initio dynamics investigation of the reaction between N2H4 and F atom, which is predicted to have three possible reaction channels. The structures and frequencies at the stationary points and the points along the minimum energy paths (MEPs) of all reaction channels were calculated at the UB3LYP/6-31+G(d, p) level of theory. Energetic information of stationary points and the points along the MEPs was further refined by means of the CCSD(T)/aug-cc-pVTZ method. The calculated results revealed that the first two primary channels (N2H4 + F -> N2H3 + HF) are equivalent and occur synchronously via the formation of a pre-reaction complex with C-s symmetry rather than via the direct H abstraction. The prereaction complex then evolves into a hydrogen-bonding intermediate through a transition state with nearly no barrier and a high exothermicity, which finally makes the intermediate further decompose into N2H3 and HF. Another reaction channel of minor role (N2H4 + F -> NH2F + NH2) was also found during the calculations, which has the same Cs pre-reaction complex but forms NH2F and NH2 via another transition state with high-energy barrier and low exothermicity. The rate constants of these channels were calculated using the improved canonical variational transition state theory with the small-curvature tunneling correction (ICVT/SCT) method. The three-parameter ICVT/SCT rate constant expressions of k(ICVT/SCT) at the CCSD( T)/aug-cc-pVTZ//UB3LYP/6-31+G(d,p) level of theory within 220-3000 K were fitted as (7.64 x 10(-9)) T (-0.87) exp(1180/T) cm(3) mole(-1) s(-1) for N2H4 + F -> N2H3 + HF and 1.45 x 10(-12) (T/298) 2.17 exp(-1710/T) cm(3) mole(-1) s(-1) for N2H4 + F -> NH2F + NH2.