Theoretical investigations on the characteristics of nanorotator assembled by C 18 and OPP are carried out from static to dynamic as follows: quantum chemical calculations of the structure and energy of supramolecular complexes to determine their stability, wave function analyses of the nature of host-guest interaction in complexes to predict the possibility of molecular rotator, and molecular dynamics (MD) simulations of the self-assembly process and ultrafast rotational behavior of supramolecular rotator. Quantum chemical calculations, wave function analyses, and MD simulations were mainly performed using Gaussian 16 (A.03) software, GROMACS 2018.8 program, and Multiwfn 3.8(dev) code, respectively. Refer to "Computational details" in the Supplemental Material for the calculation strategy of the whole work.