A series of solid solutions (Li2Fe1-yMny)SO with a cubic antiperovskite structure was successfully synthesized. The composition (Li2Fe0.5Mn0.5)SO was intensively studied as a cathode in Li-ion batteries showing a reversible specific capacity of 120 mA h g(-1) and almost a 100% Coulombic efficiency after 50 cycles at 0.1C meaning extraction/insertion of 1 Li per formula unit during 10 h. Operando X-ray absorption spectroscopy confirmed the redox activity of both Fe2+ and Mn2+ cations during battery charge and discharge, while operando synchrotron X-ray diffraction studies revealed a reversible formation of a second isostructural phase upon Li-removal and insertion at least for the first several cycles. In comparison to (Li2Fe)SO, the presence of Mn stabilizes the crystal structure of (Li2Fe0.5Mn0.5)SO during battery operation, although post mortem TEM studies confirmed a gradual amorphization after 50 cycles. A lower specific capacity of (Li2Fe0.5Mn0.5)SO in comparison to (Li2Fe)SO is probably caused by slower kinetics, especially in the two-phase region, as confirmed by Li-diffusion coefficient measurements.