In this paper we revisit the borate systems, Sr4-xBaxNa(BO3)3 and illustrate their structural relationship with the perovskite structure. In these phases, the Na and B can be considered as forming an ordered arrangement on the perovskite small cation site, with the orientation of the oxygen atoms on the borate group such that the Na is octahedrally coordinated to O. In addition, we report the preparation of a new related solid solution series, Sr4-xBaxNa1-yLiy(BO3)3, showing a complete Sr/Ba solid solution series for y ​= ​0.5. Through further investigation into Ca doping into Sr4Li(BO3)3, we have identified a new A site (Ca/Sr) ordered variant of this structure with structure refinement indicating a composition, Sr2·2Ca1·8Li(BO3)3. Thus, these borate systems represent interesting perovskite-type variants, with large oxygen deficiencies compared to a traditional perovskite brought about by ordered oxygen vacancies, and whose existence is dependent on cation ordering features. •Synthesis of solid solutions series Sr4-xBaxNa0.5Li0·5(BO3)3.•Synthesis and structure determination of new ordered Sr2·2Ca1·8Li(BO3)3 system.•Relatable to oxygen vacancy ordered perovskite structures.