The　carbon-based　metal-free　materials　as　catalysts　(named　as　carbocatalysts)　have　been　attracting　tremendous　attentions　in　electric-,　solar-　and　thermal-driven　reactions　nowadays.　Compared　to　electrocatalysis　and　photocatalysis,　the　thermal-driven　catalysis　(thermocatalysis)　including　liquid　phase　and　gas　phase　reactions　involves　wider　scope　and　is　relatively　easy　to　realize　practical　large-scale　applications.　Over　the　past　several　years,　some　striking　achievements　on　the　design　of　new　carbon-based　metal-free　materials　with　well-defined　structures　and　heteroatom　groups　as　well　as　the　revelation　of　new　reaction　mechanisms　and　active　sites　in　thermocatalysis　have　been　obtained.　However,　comparative　discussions　regarding　these　recent　achievements　have　been　rarely　highlighted.　In　this　review,　we　systematically　summarize　and　discuss　six　kinds　of　carbocatalysts　and　their　applications　in　thermocatalysis.　These　materials　include　typical　oxygen-attached　carbon,　surface　modified　carbon　(graft　with　certain　organic　compounds),　mono-doped　carbon,　co-doped　carbon,　carbon　nitride　and　materials　with　carbon　as　dopant.　Some　new　reaction　processes　as　well　as　the　related　reaction　mechanisms,　active　sites　and　intermediates　are　reviewed　critically.　Moreover,　an　outlook　on　the　in-depth　investigation　of　the　metal-free　carbocatalysis　in　the　future　is　provided.　©　2020　Science　Press