The applications of systems based on Portland Cement (PC), Calcium Aluminate Cement (CAC) and Calcium Sulphate (C)areusuallylimitedtoindoorusesinthefieldofBuildingChemistrybecausenodurabilitydataexistontheoutdooruses.TheseternarybindershavedifferentphasecompositionsandmicrostructurethanthoseoftheproductsbasedpurelyonPortlandcement.WhereasPortlandcementiswidelystudied,thereexistsverylittlepublisheddataontheperformanceofthesematerialsovertime.Thisresearchworkaimedatunderstandingthedevelopmentofthemicrostructureoftheseternarysystemsandidentifyingthedegradationmechanismsundercontrolledatmosphereandundernaturalweathering.Theinfluenceoftheformulationwasthoroughlystudiedwithrespecttohydrationmechanism,porosityandtransportproperties.SEM(BSEobservationsandEDSmicroanalysis)wasthemainanalyticaltechniquetounderstandthehydrationmechanismsandwasalsocoupledwithXRD,TGAand27AlNMR.Porositywasexaminedbysolventexchangeanddesorptionisotherm.Transportpropertieswerestudiedthroughoxygendiffusion,oxygenpermeabilityandwatersorption.Inparallel,performanceofdifferentsystemsweretestedwithrespecttothestorage,carbonation,acidcorrosionandexternalsulphateattack.Alongsidewiththatstudy,thedegradationmechanismsafter3yearsofnaturalweatheringwereexamined.ThemicrostructuralinvestigationsofthecementitiousmatrixshowthatthehydrationmechanismsofPortland−richsystemsdependonthePC/CACandCAC/C ratios but all present a delay of the silicates' hydration. The CAC-CrichbindersleadtoettringiteandAH3formation.Despitedifferenthydrationmechanisms,PortlandandCAC−C rich binder at similar porosity have similar transport properties. A first durability "map" was drawn with the data from accelerated ageing. It was found that binders containing portlandite provide superior resistance to carbonation but were more sensitive to sulphate attack, those with AH3 perform better in acidic media. The 3 years natural weathering reveals that samples underwent leaching and carbonation and the mechanical strengths remain the same from 1 to 3 years.