In this study, we aim to examine the phase behavior of inorganic/poly ((4-vinylpyridine)-block-ε-caprolactone)(P4VP-PCL) hybrids by controlling the factors including the adding amounts of inorganic species, the kinds of inorganic species and the compositions of block copolymers.Gold ions (Au3+)/P4VP-PCL hybrids were used as a model system on the phase behavior of inorganic/P4VP-PCL hybrids.Consistent to theoretical prediction, phase transformation in the hybrids with PCL-rich P4VP-PCL could be induced by the introduction of Au3+ ions.