A "smart" core shell complex is designed to combine a catalytic reaction and automatic separation through remote light control. Here, we present the induced anaphiphilic behavior of a surfactant encapsulated polyoxometalate complex With photoresponsive azobenzene units on the periphery. The reversible phase transfer of the complex shuttle between two incompatible phase termini, driven by a photoisomerization-induced polarity change, further facilitates the separation and recycle of the catalyst.