Cation and anion ordering plays an important role in the properties of materials, in particular, in the properties of perovskite materials. Here we report on unusual 5-fold cation/charge ordering in high-pressure-synthesized (at 6 GPa and,similar to 1670 K) RMn3O6 perovskites with R = Gd Tm and Y. R3+, Mn2+, and Mn3+ cations are ordered at the A site in two separate chains consisting of R3+ and alternating Mn2+ (in tetrahedral coordination) and Mn2+ (in square planar coordination), while Mn2+ and mixedvalent Mn3+ /Mn4+ are ordered at the B site in layers. The ordering can be represented as [R3+Mn0.52+Mn0.53+](A)[Mn3+Mn3.5+](B)O-6. The triple cation ordering observed at the A site is very rare, and the layered double-B-site ordering is also scarce.:RMn3O6 compounds crystallize in space group Pmmn with a = 7.2479(2) angstrom, b = 7.4525(3) angstrom, and c = 7.8022(2) angstrom for DyMn3O6 at 213 K, and they are structurally related to CaFeTi2O6. They are prone to nonstoichiometry, R1-delta Mn3O6-1.5 delta, where delta = -0:071 to -0.059 for R = Gd, delta = 0 for R = Dy, delta = 0.05-0.1 for R = Ho and Y, and delta = 0.12 for R = Er and Tim They show complex magnetic behaviors with several transition temperatures, and their magnetic properties are highly sensitive to the S values.