In this contribution, a novel solvent system for the crystallization of asiaticoside from total triterpenoid saponins of Centella asiatica was established by utilizing the difference between the induction periods of madecassoside and asiaticoside. Asiaticoside could be separated from the mixture of asiaticoside and madecassoside by crystallization with about 80% yield and 95% purity. The mechanism behind the significantly different induction periods of asiaticoside and madecassoside in the methanol + water system is also proposed. Crystallization of asiaticoside from total triterpenoid saponins of Centella asiatica achieved a maximum yield of 60% with 70% purity. A recrystallization was carried out to obtain 76% yield with 91% purity. The optimized conditions for the crystallization of asiaticoside from total triterpenoid saponins of Centella asiatica were determined.