• 1T/2H-MoS2@Co3S4 electrocatalysts were constructed by interfacial charge donation from Co to Mo atoms, resulting in formation of double heterojunctions including 1T-MoS2@Co3S4 and 2H-MoS2@Co3S4.
• Complementary effect from double heterojunctions not only triggered fast charge transport on Co–S–Mo couplings, but also enabled moderate eg orbital occupancy to adsorb oxygen-containing intermediates for efficient oxygen electrocatalysis.
• Optimal adsorption energies for solution and surface dual reaction pathways were achieved, forming two kinds of discharge product morphologies during cycling to enhance performance of Li–O2 batteries.
• The innovative heterostructure design provides a reliable strategy to construct efficient transition metal sulfide catalysts by improving electrical conductivity and modulating adsorption toward oxygenated intermediates for LOBs.