Starburst triblock copolymers consisting of 8-arm poly(ethylene glycol) (8-arm PEG), poly(L-lactide) (PLLA) or its enantiomer poly(D-lactide) (PDLA) and terminal PEG, 8-arm PEG-b-PLLA-b-PEG (Stri-L) and 8-arm PEG-b- PDLA-b-PEG (Stri-D), were synthesized. An aqueous solution of a 1:1 mixture (Stri-Mix) of Stri-L and Stri-D assumed a sol state at room temperature, but instantaneously formed a physically cross-linked hydrogel in response to increasing temperature. The resulting hydrogel exhibited a high storage modulus at 37 °C. The rapid temperature-triggered hydrogel formation, high mechanical strength, and degradation behavior render this polymer system suitable for use in injectable drug delivery system or a biodegradable scaffold for tissue engineering.