Thetransitionbetweenregularreflection(RR)andMachreflection(MR)oftypeVshock–shockinteractiononadouble-wedgegeometrywithhightemperaturenon-equilibriumeffectsisinvestigatedbyextendedshock-polarmethodandnumericalsimulation.First,thecriticalanglesoftransitionfromdetachmentcriterionandvonNeumanncriterionaredeterminedbytheextendedshock-polarmethodconsideringthenon-equilibriumeffects.Thenwavepatternsandthetransitionprocessarenumericallyobtained.Resultsofthecriticaltransitionanglesfromshock-polarcalculationandnumericalsimulationshowevidentdisagreement,indicatingtransitionmechanismbetweenRRandMRoftypeVinteractionischanged.Bycomparingwiththefrozencounterpart,itisalsofoundthatnon-equilibriumeffectsleadtoalargercriticalwedgeangleandalargerhysteresisinterval.