Lithium–sulfur (Li–S) batteries have been regarded as a promising next‐generation energy storage technology for their ultrahigh theoretical energy density compared with those of the traditional lithium‐ion batteries. However, the practical applications of Li–S batteries are still blocked by notorious problems such as the shuttle effect and the uncontrollable growth of lithium dendrites. Recently, the rapid development of electrospinning technology provides reliable methods in preparing flexible nanofibers materials and is widely applied to Li–S batteries serving as hosts, interlayers, and separators, which are considered as a promising strategy to achieve high energy density flexible Li–S batteries. In this review, a fundamental introduction of electrospinning technology and multifarious electrospinning‐based nanofibers used in flexible Li–S batteries are presented. More importantly, crucial parameters of specific capacity, electrolyte/sulfur (E/S) ratio, sulfur loading, and cathode tap density are emphasized based on the proposed mathematic model, in which the electrospinning‐based nanofibers are used as important components in Li–S batteries to achieve high gravimetric (WG) and volume (WV) energy density of 500 Wh kg−1 and 700 Wh L−1, respectively. These systematic summaries not only provide the principles in nanofiber‐based electrode design but also propose enlightening directions for the commercialized Li–S batteries with high WG and WV. A mathematic model is proposed using the electrospinning‐based nanofibers serve as a cathode and anode host, and separator to achieve high gravimetric (WG) and volume (WV) energy density of 500 Wh kg−1 and 700 Wh L−1 in Li–S batteries, respectively, by emphasizing the crucial parameters of specific capacity, electrolyte/sulfur (E/S) ratio, sulfur loading, and cathode tap density in the cell.