Abstract Elemental sulfur has been applied as soft oxidant for facile one-pot preparation of air sensitive organometallic di[5]trovacenyldichalcogenides. This methodology successfully overcomes the dilemma between air instability and the required oxidation of corresponding substrates REH or RELi (E = S, Se, Te), and also avoids the usage of unstable chlorides E2Cl2 and transition metal catalysts. The oxidation ability of various oxidizing agents including free oxygen, elemental sulfur, selenium, tellurium, hydrogen peroxide and halogen has been investigated based on their electrochemical potentials. This study provides one convenient opportunity to prepare air sensitive organometallic dichalcogenide under mild reaction condition.