Despite intensive studies on the complex perovskite Pb(Fe 2/3 W 1/3)o 3 (PFWO) relaxor, understanding the exact nature of its multifunctional properties has remained a challenge for decades. in this work we report a comprehensive structural study of the PFWO single crystals using a combination of synchrotron X-ray diffraction and high-resolution electron microscopy. The set of {h + ½, k + ½, l + ½} superlattice reflections was observed for the first time based on single-crystal synchrotron X-ray experiments (100-450 K) and transmission electron microscopy investigations, which indicates some kind of B-cation ordering in PFWO which had been thought to be totally disordered. It was found that (1) the crystal structure of PFWO should be described by a partly ordered cubic perovskite (i.e. Fm − 3m), (2) the weak ferromagnetic properties and excess magnetic moment of PFWO can be understood based on non-random distribution of Fe cations between the 4a and 4b sites, and (3) the pb displacement disorder is present in this material and the cations are probably displaced along the <100> directions. The X-ray diffraction results of this investigation show that partial cation ordering indeed exists in PFWO, which makes it necessary to revisit the generally accepted interpretations of the results obtained up to date. In agreement with X-ray diffraction study the main results of TEM study include: (1) a long range order that can be described with the Fm − 3m symmetry is reliably detected, (2) the coherence length of that long range order is in the order of 1-2 nm and (3) no remarkable chemical inhomogeneity is found in the tested PFWO crystal, excluding the possibility of a compositional ordering arising from substitutional defects in the perovskite structure. Pb(Fe 2/3 W 1/3)O 3 (PFWO) belongs to the family of Pb-based multiferroic relaxor ferroelectric complex perovskites (AB ′ 1−x B ′′ x O 3) 1-3. PFWO is formed from simple perovskite ABO 3 with the magnetic ions Fe 3+ (3d 5 , S = 5/2) and the non-magnetic ions W 6+ (5d 0 , S = 0) sharing the B-site of the perovskite-type structure. It is generally accepted that this material exhibits a disordered perovskite structure, where Fe 3+ and W 6+ ions are randomly distributed at the centers of the BO 6 octahedra 4-6. PFWO has been the subject of numerous studies due to its attractive combination of spin and dipole orderings 7-10. An interesting feature of PFWO is associated with the presence of magnetic ions Fe 3+ with a relatively high occupancy of 2/3 on the B-octahedral sites, leading to one of highest magnetic ordering temperatures established in multiferroics materials 6 , with the para-to antiferromagnetic transition occurring around T N = 340-380 K 11-14 , where the magnetic ordering is due to the superexchange interaction between the Fe ions through the O ions. Also, this material is a relaxor ferroelectric with a broad and frequency-dependent dielectric maximum (also called diffuse phase transition) around T max (or T C) = 150-200 K 15,16. Despite the 60-year history of P...