The quaternary nitrides Ca4Mg5Ge3N10 and Sr2Mg3GaN4.33 were synthesized by employing the Na azide route in weld‐shut Ta ampules. The two compounds are homotypic and crystallize in the monoclinic space group C2/m (no. 12). The crystal structures were solved and refined on the basis of single‐crystal X‐ray diffraction data [Ca4Mg5Ge3N10: a = 11.269(3), b = 3.3267(11), c = 8.008(3) Å, β = 109.80(2)°, V = 282.44(16) Å3, Z = 1; Sr2Mg3GaN4.33: a = 11.737(2), b = 3.4610(7), c = 7.8610(16) Å, β = 108.03(3)°, V = 303.65(12) Å3, Z = 1]. The three‐periodic anionic substructures of both nitrides are made up of MN4 tetrahedra with mixed occupation of central atoms M = Mg/Ge and Mg/Ga, respectively. Corner‐ and edge‐sharing of MN4 tetrahedra results in vierer and sechser ring channels along [010]. Alkaline earth metal ions are located within sechser ring channels. The crystal structures are also homeotypic with that of known Ca2MgGa3N5 and represent a more highly condensed variant of the MII2Si5N8 (MII = Sr, Ba) type of structure.