Two new quaternary selenides, namely Ba4Ga4SnSe12 and Ba6Ga2SnSe11, have been synthesized for the first time, representing the first two members in the A/M/Sn/Q (A = alkaline-earth metal; M = Al, Ga, In; Q = S, Se, Te) system. Ba4Ga4SnSe12 crystallizes in the non-centrosymmetric space group P4[combining macron]21/c of the tetragonal system and has a three-dimensional structure. Its three-dimensional framework is built up from corner-sharing GaSe4 and SnSe4 tetrahedra with eight-coordinated Ba(2+) cations residing in the cavities. Ba6Ga2SnSe11 crystallizes in a new structure type in the monoclinic centrosymmetric space group P21/c. The structure of Ba6Ga2SnSe11 features a zero-dimensional structure containing totally isolated distorted SnSe4 tetrahedra and a discrete Ga2Se7 unit with Ba(2+) cations located between them. On the basis of the diffuse-reflectance spectra, the band gaps are 2.16 (2) eV and 1.99 (2) eV for Ba4Ga4SnSe12 and Ba6Ga2SnSe11 respectively. In addition, the electronic structure calculation of Ba4Ga4SnSe12 indicates that it is a direct-gap semiconductor with the band gap mainly determined by the [Ga4SnSe12](8-) anionic framework.