The main drawback of lithium–sulfur (Li–S) batteries which leads to a short lifetime, is the shuttle effect during the battery operation. One of the solutions to mitigate the shuttle effect is the utilization of interlayers. Herein, graphene oxide (GO) paper as an interlayer has been implemented between the sulfur cathode fabricated by the vapor deposition process as a binder-free electrode and a separator in a Li–S battery in order to gain a sufficient capacity. The morphological characteristics and electrochemical performance of the fabricated electrode have been investigated. The fabricated battery demonstrates an initial discharge capacity of 1265.46 mAh g−1 at the current density of 100 mA g−1. The coulombic efficiency is obtained to be 88.49% after 40 cycles. The remained capacity for the battery is 44.70% after several cycles at different current densities. The existence of the GO interlayer improves the electrochemical properties of the battery compared to the one with a pure sulfur cathode. The obtained results indicate that after 40 cycles, the capacity retention is 2.1 times more than that of the battery without the GO implementation.