Novel bichalcogenides with the general composition (Li2TM)ChO (TM = Mn, Co; Ch = S, Se) were synthesized by single-step solid-state reactions. These compounds possess cubic anti-perovskite crystal structure with Pm (3) over barm symmetry; TM and Li are disordered on the crystallographic site 3c. According to Goldschmidt tolerance factor calculations, the available space at the 3c site is too large for Li+ and TM2+ ions. As cathode materials, all title compounds perform less prominent in lithium-ion battery setups in comparison to the already known TM = Fe homologue; e.g., (Li2Co)SO has a charge density of about 70 mAh g(-1) at a low charge rate. Nevertheless, the title compounds extend the chemical flexibility of the anti-perovskites, revealing their outstanding chemical optimization potential as lithium battery cathode material.