This paper reports the strength-promoting mechanism of alkanolamines on limestone-calcined clay cement (LC3). The hydration kinetics, phase formation and microstructure of LC3 with triethanolamine (TEA) or triisopropanolamine (TIPA) were investigated. TEA enhanced the strength of LC3, while TIPA was effective at 28 days, and a correct sulfate addition promoted their effects. Alkanolamines accelerated the aluminate reaction of LC3 during early hydration, increased sulfate slowed this reaction by producing more ettringite. TIPA favoured the hydration of ferrite in clinker, not only accelerated the silicate reaction of metakaolin, but also resulted in a rapid limestone reaction. Alkanolamines altered the morphology and chemical composition of the aluminate hydrates and C-A-S-H. Alkanolamines enabled the reduction of porosity of hardened pastes and the increased sulfate further refined them. It was the large pores being induced by TIPA at early ages that were considered to have an adverse impact on the early strength of LC3.