We report a structural evolution analysis of the long-range and local order and disorder of lead scandium niobate (PSN) down to 10 K, using a combination of neutron and x-ray diffraction on powder and single crystals. The structure of PSN is discussed and compared with those of simple perovskite compounds and . In PSN the existence of a long-range but still disordered ferroelectric phase, different from those of simple perovskites, is evidenced. The disorder of lead and scandium/niobium atoms on short-, medium- and long-range scales is discussed in connection with the dielectric properties of these materials.