With　BaCO3,　MnCO3　and　Yb2O3　as　raw　materials,　the　two　new　compounds,　12R-Ba4YbMn3O11.5　and　10H-Ba5YbMn4O14.5,　were　synthesized　using　traditional　solid-state　reaction　at　1300°C.　The　chemical　formulas　of　the　composites　were　determined　through　EDS　analysis　and　redox　titration,　the　crystalline　structure　of　the　compounds　were　determined　through　selected　area　electron　diffraction　and　Rietveld　refinement　based　on　powder　X-ray　diffraction.　It　was　shown　that　the　12R-Ba4YbMn3O11.5　belonged　to　the　R-3m　space　group　with　the　lattice　parameter　of　a　=0.578　nm　and　c=2.850　nm;　and　the　10H-Ba5YbMn4O14.5　belonged　to　the　P63/mmc　space　group　with　the　lattice　parameter　of　a　=0.575　nm　and　c　=2.377　nm.