Various different possible connection patterns of sulfate and borate tetrahedra enable a vast structural diversity in borosulfates, a rather new class of silicate-analogous compounds. Here we unravel a direct relationship from S-O-S to B-O-S to B-O-B bridges for the first time in borosulfate chemistry. Solvothermal synthesis in pure oleum (65% SO3) yielded the first alkaline earth metal borosulfate comprising S-O-S bridges: Ba[B(S2O7)(2)](2) (I2/a , Z = 4, a = 1160.77(9) pm, b = 891.44(7) pm, c = 2130.26(19) pm, beta= 104.0341(17)degrees) contains molecular [B(S2O7)(2)](- )anions of a central boron atom and two chelating disulfate groups. By using equal amounts of sulfuric acid and oleum solely B-O-S bridges were obtained in Ba[B-2(SO4)(4)] (Pnna, Z = 4, a = 1279.08(18) pm, b = 1280.0(2) pm, c = 731.70(11) pm) featuring one-dimensional 1(infinity)[B(SO4)(4/2)](-) chains. The thermal analysis on Ba[B(S2O7)(2)](2) revealed the conversion from S-O-S bridges to B-O-S bridges in Ba[B-2(SO4)(4)] and to B-O-B bridges in Ba[B2O(SO4)(3)] by a successive release of SO3. Thus, BaO-B2O3-SO3 is the first quaternary system for borosulfates uniting all three possible connection patterns enabling us to understand the fascinating but systematic chemistry in such systems. Both new compounds were also characterized by means of X-ray powder diffraction, electrostatic calculations, and infrared spectroscopy assisted by density functional theory (DFT).