With the advancement of nanotechnology and material chemistry, micelles have emerged as one of the most attractive carriers for anticancer drug delivery. In this study, a newly developed polymerization technique termed as “sequential ring-opening polymerization (SROP)“ was used to synthesize poly (ethylene glycol)-block-polylactide-block-polylactide (PEG-PLA-PLAs). Utilizing the features of SROP, well-controlled chain length of two different PLA blocks by using PEG as initiator can be achieved. Two types of PEG-PLA-PLAs, PEG-PLA11-PLA11 and PEG-PLA18-PLA18, were successfully synthesized and characterized. Having amphiphilic properties, PEG-PLA-PLAs were used to form micelles through self-assembly. The effects of PLA length on the resultant micelles were thoroughly investigated.