Architecture-regulated cellulose derivatives were prepared by regioselective substitution of C-2, -3, and -6 position hydroxyls in cellulose by O-acetyls or trityls. Their dynamic structures formed in polar solvents were compared with those by the commercial cellulose acetates where the distribution of hydroxyls and O-acetyls was nearly random in the chain. Tt was found that the difference in the chain architecture induces a large difference in the chain conformation, the solubility, and the clustering mechanism and structures; i.e., they changed with solvent quality, concentration, temperature, strength of external field, and so on.