A substitution for Cu by a 3d-metal (Fe, Co, Mn) in the superconducting Bi phases (Bi2Sr2Can−1CunOy; n = 1,2 and 3) has led to the discovery of new phases. These 3d-metal substituted phases are non-superconducting and, in contrast to the Cu-based phases, they exhibit a structural modulation that is commensurate. Single crystal x-ray studies were performed on the Bi2Sr3Fe2Oy, Bi2Sr2CoOy and Bi2Sr2MnOy compounds. A result, in common, is that the modulation is caused by the periodic insertion of a row of oxygen atoms in the Bi layers and this results in a corrugated-like slab structure. The Bi-O layers can be described as composed of alternating rocksalt-type and oxygen deficient perovskite-type blocks. For the Fe (n=2) phase the Bi atoms form ribbons (chains) in the ab plane. This is in contrast to the n=1 Co or Mn phases for which a disorder at the oxygen position is observed. Although the extra oxygen in the Bi-O layer could account for the doping mechanism in the high Tc Bi-phases, cation non-stoichiometry may also beimportant.