High-temperature pyrolysis of waste tires is a promising method to produce high-quality carbon black. In this study, carbon black formation characteristics were investigated during tire pyrolysis at 1000-1300°C with residence times of <1s, 1-2s, and 2-4s. It is shown that with temperature increasing from 1000°C to 1300°C carbon black yield was increased from 10% to 27% with residence times of 2-4s. Carbon black exhibited a core-shell nanostructure over 1100°C and the graphitization degree was promoted with the temperature and residence time. While the mean particle diameter decreased with the temperature to 69nm at 1300°C and further increased by residence time. The molecular-level evolution from tire to initial carbon black was further revealed by reactive force field molecular dynamics simulations. Light oil, gas, and radicals were transformed to initial cyclic molecules and long carbon chains via carbon-addition-hydrogen-migration, H-abstraction-C2H2-addition, and radical-chain reactions, subsequently forming PAHs. The coupling of PAHs aliphatic side chains formed large graphene layers that gradually bent to fullerene-like cores and generated incipient carbon black. The process mechanism from volatiles evolution to carbon black was proposed, which may be helpful for obtaining high-quality carbon black from high-temperature pyrolysis of waste tires.