Noble gas complex fluorides exhibit many interesting structural features, which worthies a detail study. We report the results of the quantum chemical calculations of complex xenon fluorides, XeF₅AF₆ (A = As, Sb, Bi, V, Nb, Ta). Software package AIMPAC was modified to provide a calculation of the electron localization function (ELF) and topological analysis of this function. All the bond critical points in the electron density of these compounds possess a positive value of Laplacian of the electron density: that is typical for closed-shell atomic interactions. It was found that ELF of molecules XeF₅⁺VF₆^-, XeF₅⁺NbF₆^- and XeF₅⁺TaF₆^- exhibits 13 core attractors, i.e. C(A), C(Xe) and C(F1-11), 5 valence disynaptic attractors V(Fi,Xe) sited on Fi-Xe bonds (i = 1-5) and valence monosynaptic attractors V(F1-5), two per each F atoms. The later attactors provide a week bond between F and Xe atoms of adjacent molecules an explain the spatial organization the molecular ensembles and clusters in solids. It was demonstrated that the ELF value of disynaptic attractors V(Xe,F₆) increased in series V-Nb-Ta and As-Sb-Bi together with the bond distances. Simultaneously, the bond strength and reactivity of substances decrease.