Superlattices　are　rising　stars　on　the　horizon　of　energy　storage　and　conversion,　bringing　new　functionalities;　however,　their　complex　synthesis　limits　their　large-scale　production　and　application.　Herein,　a　simple　solution-based　method　is　reported　to　produce　organic–inorganic　superlattices　and　demonstrate　that　the　pyrolysis　of　the　organic　compound　enables　tuning　their　interlayer　space.　This　strategy　is　exemplified　here　by　combining　polyvinyl　pyrrolidone　(PVP)　with　WSe2　within　PVP/WSe2　superlattices.　The　annealing　of　such　heterostructures　results　in　N-doped　graphene/WSe2　(NG/WSe2)　superlattices　with　a　continuously　adjustable　interlayer　space　in　the　range　from　10.4　to　21　Å.　Such　NG/WSe2　superlattices　show　a　metallic　electronic　character　with　outstanding　electrical　conductivities.　Both　experimental　results　and　theoretical　calculations　further　demonstrate　that　these　superlattices　are　excellent　sulfur　hosts　at　the　cathode　of　lithium–sulfur　batteries　(LSB),　being　able　to　effectively　reduce　the　lithium　polysulfide　shuttle　effect　by　dual-adsorption　sites　and　accelerating　the　sluggish　Li–S　reaction　kinetics.　Consequently,　S@NG/WSe2　electrodes　enable　LSBs　characterized　by　high　sulfur　usages,　superior　rate　performance,　and　outstanding　cycling　stability,　even　at　high　sulfur　loadings,　lean　electrolyte　conditions,　and　at　the　pouch　cell　level.　Overall,　this　work　not　only　establishes　a　cost-effective　strategy　to　produce　artificial　superlattice　materials　but　also　pioneers　their　application　in　the　field　of　LSBs.　©　2022　Wiley-VCH　GmbH.