For the first time possible reaction pathways of superelectrophilic polycondensation of 2,2,2-trifluoroacetophenone and biphenyl in trifluoromethanesulfonic acid (TSFA) have been studied theoretically at B3LYP/aug-cc-pvtz(-f)//B3LYP/6-31G* level. The reaction graph reveals the existence Of four different reaction routes for polycondensation process. The analysis of the reaction pathways shows that kinetically most favorable pathway involves the successive reaction between protonated 2,2,2-trifluoroacetophenone and neutral oligomers. The reactivity indexes best Correlated with calculated thermodynamic and kinetic parameters are these based on the energy difference between the ionization potential of a nucleophile and the electron affinity of a electrophile showing correlation coefficients up to 0.95. These reactivity indexes call be Successfully used for the prediction of the most favorable reaction pathways in the superelectrophilic polycondensation. The calculations established basic rules for efficient design of monomers for superelectrophilic polycondensation. (c) 2005 Elsevier Ltd. All rights reserved.