A new synthetic approach is suggested for preparation of layered rare-earth oxide compounds containing [Ln(2)O(2)] slices and molecular anion sheets (CO32-, SO42-, and CrO42-). It is based on exchange reactions of rare-earth oxychlorides, [Ln(2)O(2)]Cl-2, and alkali carbonates, sulfates, or chromates. Five new rare-earth oxychromates [Ln(2)O(2)]CrO4 (Ln = Pr-Gd) have been prepared which adopt a new, probably layered, structure type. In addition, significantly easier and more efficient synthetic pathways were found to the known compounds [Ln(2)O(2)]K-2(CO3)(2) and [La2O2]CrO4. The structure of the latter compound has been determined from neutron powder diffraction data. Factors affecting reaction pathways and products are discussed, as well as prospects for applying the approach to more complex layered compounds.