Increased synthetic control in borosulfate chemistry leads to the access of various new compounds. Herein, the polymorphism of phyllosilicate-analogous borosulfates is unraveled by adjusting the oleum (65 % SO3) content. The new polymorphs beta-Mg[B-2(SO4)(4)] and alpha-Co[B-2(SO4)(4)] both consist of similar layers of alternating borate and sulfate tetrahedra, but differ in the position of octahedrally coordinated cations. The alpha-modification comprises cations between the layers, whereas in the beta-modification cations are embedded within the layers. With this new synthetic approach, phase-pure compounds of the respective polymorphs alpha-Mg[B-2(SO4)(4)] and beta-Co[B-2(SO4)(4)] were also achieved. Tanabe-Sugano analysis of the Co(2+)polymorphs reveal weak ligand field splitting and give insights into the coordination behavior of the two-dimensional borosulfate anions for the first time. DFT calculations confirmed previous in silico experiments and enabled an assignment of the polymorphs by comparing the total electronic energies. The compounds are characterized by single-crystal XRD, PXRD, FTIR, and UV/Vis/NIR spectroscopy, thermogravimetric analysis (TGA), and density functional theory (DFT) calculations.