Although　lithium–sulfur　(Li–S)　batteries　are　among　the　most　promising　rechargeable　batteries　in　the　field　of　energy-storage　devices,　their　poor　cycling　performance　restricts　their　potential　applications.　Polar　materials　can　improve　the　cycling　stability　owing　to　their　inherent　strong　chemical　interaction　with　polysulfides.　Herein,　novel　rutile　TiO2　mesocrystals　(RTMs)　are　employed　as　the　host　for　sulfur　in　Li–S　batteries;　the　RTMs　display　a　stable　cycling　performance　with　a　capacity　retention　of　64　%　and　a　small　average　capacity　decay　rate　of　0.12　%　per　cycle　over　300　cycles　at　1　C　rate.　The　good　electrochemical　properties　are　attributed　to　the　interior　ordered　nanopores　of　the　RTMs,　which　can　effectively　limit　the　dissolution　of　polysulfides,　and　the　ultrafine　nanowires　in　RTMs,　which　shorten　the　path　for　lithium-ion　transport　effectively.　©　2017　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.