Complementary theoretical and experimental studies of the consecutive steps of superacid catalyzed polyhydroxyalkylation reactions have been carried out. Calculations for the superacid catalyzed polyhydroxyalkylation of trifluoroacetone and trifluoroacetophenone with aromatic hydrocarbons explained a number of experimental facts within a single theoretical framework of monoprotonation. The principal factors affecting kinetics of superacid mediated hydroxyalkylation were shown to be as follows: (i) the acidity of the superacid affecting protonation energy of carbonyl components; (ii) the electrophilicity of carbonyl components; and (iii) the nucleophilicity of aromatic components. The modification of those factors allows for timing of the reactivity of carbonyl and aromatic components; thereby, reaction kinetics are controlled. The conclusions were confirmed by the experiments. Theoretically predicted stoichiometrically imbalanced polymerizations of trifluoroacetone, trifluoroacetophenone, octafluoroacetophenone, and isatin with nonactivated, aromatic hydrocarbons gave high-molecular-weight polymers with a very small excess of the carbonyl compound. The main reasons contributing to the polymerization accelerations were found to be an increase of the first, rate-determining step reaction, and a high efficiency of the superacid catalyzed polyhydroxyalkylations. The present work has thus opened a new route to preparations of polymers of linear, hyperbranched, or hybrid (e.g.. linear hyperbranched) architecture by operating on structural parameters and reaction conditions.