Oxychalcogenides are emerging as promising alternative candidates for a variety of applications including for energy. Only few phases among them show the presence of Q–Q bonds (Q = chalcogenide anion) while they drastically alter the electronic structure and allow further structural flexibility. Four original oxy(poly)chalcogenide compounds in the system Ba–V–Q–O (Q = S, Se) were synthesized, characterized, and studied using density functional theory (DFT). The new structure type found for Ba 7V 2O 2S 13, which can be written as Ba 7S(VS 3O) 2(S 2) 3, was substituted to yield three selenide derivatives Ba 7V 2O 2S 9.304Se 3.696, Ba 7V 2O 2S 7.15Se 5.85, and Ba 7V 2O 2S 6.85Se 6.15. They represent original multiple-anion lattices and first members in the system Ba–V–Se–S–O. They exhibit in the first layer heteroleptic tetrahedra V 5+S 3O and isolated Q 2– anions and in the second layer dichalcogenide pairs (Q 2) 2– with Q = S or Se. Selenide derivatives were attempted by targeting the selective substitution of isolated Q 2– or (Q 2) 2– (in distinct layers) or both by selenide, but it systematically led to concomitant and partial substitution of both sites. A DFT meta-GGA study showed that selective substitution yields local constraints due to rigid VO 3S and pairs. Experimentally, incorporation of selenide in both layers avoids geometrical mismatch and constraints. In such systems, we show that the interplay between the O/S anionic ratio around V 5+, together with the presence/nature of the dichalcogenides (Q 2) 2– and isolated Q 2–, impacts in unique manners the band gap and provides a rich background to tune the band gap and the symmetry.