The pH- and temperature-responsive behavior of amphiphilic block copolymer poly(L-lactide)-b-poly(2-(dimethylamino)ethyl methacrylate) (PLLA-b-PDMAEMA) in aqueous solutions is investigated using static and dynamic light scattering. Electrostatic force, hydrophobic interaction, and hydrogen bonding coexist in the system. Micelles with different structures are prepared using water addition (WA) and direct dissolution (DD) methods. The aggregation from loose micelles into large micellar dusters is observed above the transition temperature under basic conditions. Only micellar clusters from the DD method could disaggregate when temperature was decreased to 24.3 degrees C after heating. The behavior of the micelles prepared with the DD method indicates that only the outer parts of the PLLA-b-PDMAEMA chains in the corona are solvated.