In this work, we report a rational design and facile synthetic process for the construction of a 3-dimensional N, S co-doped reduced holey graphene oxide/carbonized cellulose paper as interlayer in Li–S batteries. The interlayer has a labyrinth-like structure with plenty of nanosized holes to achieve the permselectivity for Li ions and effective intercept for polysulfides. The coin cell with the interlayer shows a high initial discharge capacity of 1263.5 mAh/g at 0.2 C, a low capacity fading rate of 0.0487% per cycle for 300 cycles at 1 C, and an excellent rate performance of 864.6 mAh/g at 2 C. Moreover, this cell also has excellent anti-self-discharge property and a high areal capacity of 6.1 mA h/cm2 at a sulfur loading of 8.1 mg/cm2 using aluminum foil as the current collector. Thus, this work suggests the permselective and multifunctional interlayer as a practical and effective strategy for the application in the high-performance Li–S battery.