© The Royal Society of Chemistry. Two series of crystals were prepared via Sn flux synthesis with the compositional fluxes of Yb14-xLnxMnSb11, where x = 0.1-0.9 and x = 0.4. By X-ray structural measurements and microprobe analysis, the maximum amount of Ln incorporated in the unit cell matrix were determined to be 0.37 ± 0.04 for the La-Nd and 0.45 ± 0.04 for Sm-Tm elements with solid substitution solution formation. The Ln incorporation did not change the unit cell significantly but the cell volume decreased going from the largest La-Nd to the smallest Tm-Lu cations. The Ln0.30-0.40 samples demonstrated congruent melting and their melting points increased by ∼30-50 °C compared to the pristine matrix. The temperatures were attributed to the ordered structural state due to the Ln distribution in the unit cell only through the one regular system site. Based on geometrical fitting between crystal radii of Yb2+ and Ln3+ in six-coordination, the Yb(2) sites were found to be more preferable for substitution by La-Nd, Yb(1) by Sm-Ho and Yb(3) by Tm and Lu atoms. Thermal losses as a temperature function of the alloyed by La and Lu samples were determined by a step-by-step heating procedure with analysis of the vapor condensate deposited on the viewing window of the chamber. This experiment demonstrated a high mobility of the tetrahedral Mn and Sb along with Yb ions in the Yb14MnSb11 matrix with incongruent sublimation beyond 1300 °C and a decrease of the thermal weight losses by half if the matrix was alloyed by La. Occupation of the Yb sites by Ln atoms varied the geometry of the MnSb4 tetrahedron as well as electron properties and bonding in this structural fragment, and these changes are considered in the context of the coupling between chemical structure and thermal stability of the compounds. The improved thermal stability due to increasing the total ionic state of the alloyed samples was found to possibly be a useful factor for the long-time use of these materials for space applications.