We report here on the characterization of the vacancy-ordered perovskite-type structure of BaFeO2.5 by means of combined Rid-veld analysis of powder X-ray and neutron diffraction data. The compound crystallizes in the monoclinic space group P2(1)/c [a = 6.9753(1) angstrom, b = 11.7281(2), c = 23.4507(4) angstrom, beta = 98.813(1)degrees, and Z = 28] containing seven crystallographically different iron atoms. The coordination scheme is determined to be Ba7(FeO4/(2)),(FeO3/2O1/1)(3)(FeO5/2)(2)(FeO6/2)(1) = Ba7Fe1[6],(Fe2Fe4O17.5)-Fe-[4]-O-[4] and is in agreement with the Fe-57 Mossbauer spectra and density functional theory based calculations. To our knowledge, the structure of BaFeO2.5 is the most complicated perovskite-type superstructure reported so far (largest primitive cell, number of ABX(2.5) units per unit cell, and number of different crystallographic sites). The magnetic structure was determined from the powder neutron diffraction data and can be understood in terms of "G-type" antiferromagnetic ordering between connected iron-containing polyhedra, in agreement with field-sweep and zero-field-cooled/field-cooled measurements.