© 2020 Elsevier Ltd 3D printing has stimulated burgeoning interest in customized design of sulfur cathodes for Li–S batteries targeting advanced electrochemical performances. Nevertheless, the prevailing 3D-printed sulfur electrodes are solely based on carbonaceous materials; constructing electrocatalyst-equipped cathode to help expedite sulfur redox kinetics remains unexplored thus far. Herein, we develop a free-standing sulfur cathode via 3D printing using hybrid ink encompassing sulfur/carbon and metallic LaB6 electrocatalyst. Such unique architectures with optimized Li /e− transport and ample porosity are in favor of efficient polysulfide regulation. Accordingly, an initial capacity of 693 mAh g−1 can be achieved at 6.0C accompanied by a low capacity fading rate of 0.067% per cycle over 800 cycles (with a sulfur loading of 1.5 mg cm−2). To envisage practical applications, elevated sulfur loadings from 3.3 to 9.3 mg cm−2 are further evaluated. Our study marks the first-time investigation on the introduction of efficient electrocatalyst into the printable ink for the construction of 3D-printed Li–S battery harnessing high rate capability and areal capacity.