Abstract The complex oxide Sr 11Re 4O 24 has been synthesized and its crystal structure was determined by a combination of X-ray powder analysis (space group I4 1/ a; a=11.6779(1) Å, c=16.1488(2) Å; Z=4) and electron diffraction. Refinement of the crystal structure was carried out using neutron powder diffraction data ( χ 2=1.85). The compound has a cation-deficient perovskite-related structure where cation vacancies are located at the A-sublattice. Re and Sr atoms occupy B-positions in an ordered “rock-salt” manner. The perovskite framework is strongly distorted due to rotation of ReO 6 octahedra, leading to a formation of the eightfold coordination for Sr atoms in B-positions. An ordered arrangement of Re +6 and Re +7 cations is proposed on the basis of different average Re–O distances. The Sr 11Re 4O 24 structure could be considered as a Ca 11Re 4O 24 type of perovskite structure distortion. A magnetic order of Sr 11Re 4O 24 (ferro- or ferrimagnetic) is observed from SQUID measurements ( T C=12.0 K). A moment of μ=0.80 μ B is derived from the paramagnetic region (30–200 K) for Re 6+.