<p>The crystal structures of new layered manganese bismuth tellurides with the compositions Mn0.85(3)Bi4.10(2)Te7 and Mn0.73(4)Bi6.18(2)Te10 were determined by single-crystal X-ray diffraction, including the use of microfocused synchrotron radiation. These analyses reveal that the layered structures deviate from the idealized stoichiometry of the 12<i>P</i>-GeBi4Te7 (space group <i>P</i>3<i>m</i>1) and 51<i>R</i>-GeBi6Te10 (space group <i>R</i>3<i>m</i>) structure types they adopt. Modified compositions Mn1–<i>x</i>Bi4+2<i>x</i>/3Te7 (<i>x </i>= 0.15 – 0.2) and Mn1–<i>x</i>Bi6+2<i>x</i>/3Te10 (<i>x </i>= 0.19 – 0.26) assume cation vacancies and lead to homogenous bulk samples as confirmed by Rietveld refinements. Electron diffraction patterns exhibit no diffuse streaks that would indicate stacking disorder. The alternating quintuple-layer [M2Te3] and septuple-layer [M3Te4] slabs (M = mixed occupied by Bi and Mn) with 1:1 sequence (12<i>P </i>stacking) in Mn0.85Bi4.10Te7 and 2:1 sequence (51<i>R </i>stacking) in Mn0.81Bi6.13Te10 were also observed in HRTEM images. Temperature-dependent powder diffraction and differential scanning calorimetry show that the compounds are high temperature phases, which are metastable at ambient temperature. Magnetization measurements are in accordance with a MnII oxidation state and point at predominantly ferromagnetic coupling in both compounds. The thermoelectric figures of merit of n-type conducting Mn0.85Bi4.10Te7 and Mn0.81Bi6.13Te10 reach <i>zT </i>= 0.25 at 375 °C and <i>zT </i>= 0.28 at 325 °C, respectively. Although the compounds are metastable, compact ingots exhibit still up to 80% of the main phases after thermoelectric measurements up to 400 °C.</p>