The present study investigates the working principle upon the accelerating-retarding effect of triethanolamine dosage on the initial setting time of hydrated cement. We have conducted atomistic simulation to probe the molecular interactions between triethanolamine and dissolved ions of hydrated cement and have performed experiment to examine the effect of triethanolamine upon cement hydration. It is found that the accelerating-retarding effect of triethanolamine on the initial setting time is caused by the different intensity of formed ettringite, which is governed by the triethanolamine dosage. This finding provides the piece of insight information on the roles of triethanolamine and ettringite formation upon the initial setting time.