We have calculated the electron and positron impact ionization of a set of molecules, SF6−nHn(n=0−6), SCln(n=1−6) , SFn−1Cl(n=1−6) and SF5X(X=CN,CFO), for which there are much fewer data in the literature. We have optimized the targets, and their electric polarizability is calculated along with their orbital binding and kinetic energies within the Hartree–Fock approximation that serve as input to the Binary Encounter Bethe (BEB) model for both electron and positron ionization. Most of the targets are investigated for the first time, apart from SF6, for which we compared our data with various experimental and theoretical data, giving us a good comparison.