Electronic, structural, and spectroscopic properties of the ground-state neutral and singly ionized mono-, di-, tri-, and tetrafluoropyrroles are studied using ab initio and density functional theory quantum mechanical methods. The effects of the number and position of the substituents on the electrochemical properties of the pyrrole ring have been studied. Using the optimized structures obtained for these molecules and their cations, IR and NMR spectra have been calculated and analyzed. The results of this study, including charge- and spin-density distribution analyses, show that among all of these compounds 3-fluoropyrrole and 3,4-difluoropyrrole have the most suitable conditions for electropolymerization.