This study investigated the influence of limestone (LS) and calcium sulfate (C)mineraladditivesonthehydrationkineticsofhigh−α−Al2O3calciumaluminatecement(CAC)utilizingexperimentaltechniquesandthermodynamicsimulations.Increasingthereplacementleveloflimestoneorcalciumsulfateincreasedthecumulativeheatofthehydrationreaction.ThelimestoneexhibitedlimitedacceleratoryeffectstotheCAChydrationkineticsduetothecoarsenessofthepowder.Thecoarseparticlesizedistributionlimitedanyheterogenousnucleationthatwouldhaveoccurredwithafinerparticlesizeaswellastheintrinsicinsolubilitykineticallylimitstheformationofmonocarboaluminatephases.Conversely,thecumulativeheatreleaseincreasedasthelimestonecontentincreased;however,thiswasnotduetoanyenhancedreactivityprovidedbythelimestone.Instead,thisincreaseinthecumulativeheatisduetoacombinationoftheLSandtheincreaseintheamountofwateravailabletoreactwithCACviathedilutioneffect.Incomparison,theincreaseintheC replacement level accelerated the heat flow rate of CAC with the Cparticlesactingasafavorablesurfaceforheterogenousnucleationofthehydratesduringtheinitialstagesofthehydrationreaction.IncreasingtheC replacement level does not form more ettringite and does not translate in an increase in the compressive strength. After the 72-h hydration period, Cremainsinthemicrostructure,showingthatthecompletedissolutionofC is not responsible for the monotonic increase in heat flow rate. It is expected that the amount of hydrates or residual unreacted particles cannot compensate for the decrease in strength caused by the reduction of α-Al2O3 present in the CAC