Polyoxometalates (POMs)

as a kind of inorganic cluster containing various transition metal elements

have attracted tremendous attentions due to its defined structures and diverse properties in optical

electric

magnetic

catalytic

and biological areas. The combination of POMs and block copolymers could not only improve the processability of POMs which is one of the common obstacles for most inorganic materials in practical applications

but also endow the hybrids with new properties

i.e. stimuli-responsive properties. POMs/block copolymer hybrid materials could be built up through noncovalent and covalent interactions. Compared with covalent interactions

diverse noncovalent interactions could endow hybrid materials with flexibility and responsiveness. The individual properties of POMs and block copolymers could be integrated and magnified through noncovalent interactions. In this review

the fabrication strategy of POMs/block copolymers hybrid materials through noncovalent interactions and especially the stimuli-responsive hybrid systems were introduced. In the first part of this review

the fabrication strategies of the hybrids through noncovalent interactions were comprehensively summarized. Electrostatic attractions as a dominative driving force have been widely used to establish hybrids based on the anionic POMs and the cationic block polymers in a straightforward way. Besides

covalent bonds and H-bonding interactions were also introduced into hybrids establishment based on the electrostatic interactions

further enriching the fabrication strategies and assembling behaviors. Diverse morphologies

like micelles

vesicles

fibers

tubes

rings

films

and gels

would be observed through various strategies. In the second part

the stimuli-responsive behaviors of POMs/block copolymers based hybrids were introduced. The changes of physicochemical properties of both block copolymers and POMs could be triggered by extra stimuli such as pH

gas

and electrical signals. The stimuli-responsiveness of block copolymer and/or POMs could not only alter the assembling behaviors of hybrids

but also create new functions which could be accomplished by none of the individual component. By integrating the advantages of block copolymers and POMs

this kind of hybrid materials has a promising future in realms of biomaterials

sensors

and smart materials.