A temperature-dependent structural investigation of the substituted argyrodite Ag(7)GeSe(5)I has been carried out on a single crystal from 15 to 475 K, in steps of 50 K, and correlated to its conductivity properties. The argyrodite crystallizes in a cubic cell with the F\bar 43m space group. The crystal structure exhibits high static and dynamic disorder which has been efficiently accounted for using a combination of (i) Gram-Charlier development of the Debye-Waller factors for iodine and silver, and (ii) a split-atom model for Ag(+) ions. An increased delocalization of the mobile d(10) Ag(+) cations with temperature has been clearly shown by the inspection of the joint probability-density functions; the corresponding diffusion pathways have been determined.