Understanding the kinetics during the metal-insulator transition process is crucial to sort out the underlying physical nature of electron-lattice interactions in correlated materials. Here, based on the temperature-dependent in situ x-ray absorption fine structure measurement and density-functional theory calculations, we have revealed that the monoclinic-to-tetragonal phase transition of VO2 near the critical temperature is characterized by a sharp decrease of the twisting angle δ of the nearest V-V coordination. The VO2 metallization occurs in the intermediate monoclinic like structure with a large twist of V-V pairs when the δ angle is smaller than 1.4°. The correlation between structural kinetics and electronic structure points out that the structural rearrangement is a key factor to narrow the insulating band gap.