Reaction of perfluoroquinoline 1 and perfluoroisoquinoline 2 with benzylamine gave mono- and di-aminated quinoline and isoquinoline systems, respectively, depending upon the reaction conditions by selective SNAr processes. Optimised model geometries of the aminated derivatives at MP2/6-31G* were in very good agreement with available X-ray crystallographic data and were used to compute 19F and 13C GIAO-NMR shifts. Comparison with observed 19F and 13C NMR shifts give excellent correlations, indicating that 19F and 13C GIAO-NMR computations are powerful tools in structurally identifying polyfunctional, polycyclic perfluoroheteroaromatic compounds and aiding NMR resonance assignment.