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 system-atically 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.