Aminated poly(vinyl chloride)s (AmPVCs) were synthesized for use as fixed-site proton carrier membranes. Reactions between PVC and methylpiperazine (MePIP) in dimethylformamide (DMF) were studied using UV-VIS spectroscopy over time, temperature, and in the presence of the catalyst, potassium fluoride (KF). Based on the spectra of AmPVCs in THF, the peak attributions were assigned and the extinction coefficients were calculated to determine the vinyl MePIP groups and polyenes with different number of conjugated double bonds (n). The rate constants for the accumulation of vinyl MePIP groups (k(N)), polyenes with 2 less than or equal to n less than or equal to 7 (k(n)), and total conjugated double bonds (k(D)) were calculated at 90 degrees C. The k(N) constant was only about one half as much as k(D), and k(n) > k(n+1) (for 2 less than or equal to n less than or equal to 7). Assuming an Arrhenius relationship, the activation energies (Gamma E) were calculated for the formation of the vinyl MePIP groups and polyenes with 2 less than or equal to n less than or equal to 13 over different temperature ranges and in the presence or absence of KF. The first double bond formation was always favoured over the substitution reaction at any temperature and were independent of the presence of KF. As for the propagation of double bonds, short chains grew easier than long chains; but after a certain n, they grew with the same energy barrier. When the EMF-pH responses of AmPVC membranes were studied, no clear dependence was observed between the Nernstian responses of the membranes and the amount of conjugated double bonds (D) or the D/R-N, where R-N was the amount of vinyl MePIP groups. Nemstian responses were obtained for membranes made from AmPVCs with 0.003 less than or equal to R-N less than or equal to 0.04 and 0.6 less than or equal to D/R-N less than or equal to 1.7.