Amphiphilic block copolymers have attracted increasing attention due to their potential applications in controlled release and biotechnology. The self-assembled aggregates consisit of a hydrophobic core and hydrophilic shell to produce a vehicle suitable for delivering hydrophobic drugs. In addition, stimuli-responsive polymers can be triggered by external factors and give rise to the corresponding physical and/or chemical changes. So far reports concerning the supramolecular assembly between two or more kinds of block copolymers are limited. In this work, supramolecular assembly of binary block copolymers of PEO-b-PMAA and PEO-b-PMAZO in the selective solvent was investigated.