We investigate the structural, vibrational, and electrical transport properties of nanocrystalline rutile and its high-pressure polymorphs by Raman spectroscopy, and AC complex impedance spectroscopy in conjunction with the high-resolution transmission electron microscopy (HRTEM) up to similar to 25.0 GPa using the diamond anvil cell (DAC). Experimental results indicate that the structural phase transition and metallization for nanocrystalline rutile occurred with increasing pressure up to similar to 12.3 and similar to 14.5 GPa, respectively. The structural phase transition of sample at similar to 12.3 GPa is confirmed as a baddeleyite phase, which is verified by six new Raman characteristic peaks. The metallization of the baddeleyite phase is manifested by the temperature-dependent electrical conductivity measurements at similar to 14.5 GPa. However, upon decompression, the structural phase transition from the metallic baddeleyite to columbite phases at similar to 7.2 GPa is characterized by the inflexion point of the pressure coefficient and the pressure-dependent electrical conductivity. The recovered columbite phase is always retained to the atmospheric condition, which belongs to an irreversible phase transformation.