Variousagriculturalcropresiduesincludingcornstover,corncob,andsorghumstalkwithamoisturecontentof75wt%weresubjectedtoalongpretreatment(12-60h)withsupercriticalCO2(scCO2),atlowtemperature(50-80℃)andapressureof17.5-25.0Mpa.Thesugaryieldsfromtheenzymatichydrolysis(EH)ofthepretreatedsampleswereasmuchasthree-tofourfoldgreaterthanthoseaffordedbytherawmaterials.However,whenpretreatmentwasconductedwithinashorttime(e.g.0.5h),aspreviouslyreportedintheliterature,onlyaslightincreaseintheEHsugaryieldswasobserved.TheproposedscCO2pretreatmentmechanismdemonstratedtheroleofmoistureinthesystem.Wetting,softening,andswellingwereobservedtomainlyaffectthelignocellulosewhenasuitableamountofwaterwasadded.Finally,thesampleswereanalysedbyX-raydiffractionandscanningelectronmicroscopy,beforeandafterpretreatment,toinvestigatethechangesinthemicroscopicstructureofthebiomass.