We designed and synthesized a series of microphase separated ABA triblock copolymers containing inner soft poly[2,5-di(n-hexoxycarbonyl)styrene](PHCS)block and outer hard poly(4-vinylpyridine)(P4VP)block by ATRP.Their microphase separated phase behavior was investigated with various experimental techniques.With the P4VP volume fraction less than 20%,the triblock copolymers exhibit ordered cylindrical or spherical morphologies with hard P4VP domains surrounded by continuous phase of soft PHCS matrix.By introducing the metal-ligand coordination interaction between P4VP and Zn2+,we prepared the hybrid of the triblock and zinc perchlorate(Scheme 1).With increasing the amount of zinc perchlorate to the cylindrical phase of V30H123V30(V denotes P4VP and H denotes PHCS),the X-ray data of the sample displays a disrupt shift of the 1st scattering peak to lower q value after complexation.Increasing the mole ratio of Zn2+/VHV from 1:18 to higher value of 1:6 leads to cylinder-lamellae phase transition since the q-ratio of the first two scattering varies from 1:√3 to 1:2,and this transition is further confirmed by TEM(Figure 1).The strong metal-ligand association results in the increase of volume fraction of P4VP domains,as well as the change of incompatibility between different blocks,which causes the domain size expansion and morphologies transformation.