To enrich the building blocks and functions of supramolecular polymer, functioned inorganic polyoxometalate clusters were introduced through a novel and efficient orthogonal self-assembly strategy. The design principle is based on the organic modification of polyoxometalates (POMs) with coordination groups and electrostatic interaction of POMs with surfactants capped by photo-cross-linkable groups. Because of the relatively independent nature of these two interactions, it is possible to prepare POMs-based supramolecular cross-linked network through coordination- photo-cross-linking and vice versa, leading to the formation of main-chain-type POMs-based supramolecular polymer networks and gels. The responsiveness of these two interactions also endows the resulted supramolecular polymer with different responsiveness to light and coordination. Therefore, orthogonal self-assembly supramolecular polymerization of POMs provides a facile strategy to improve the processability of inorganic clusters, paving a new avenue toward cluster-based materials and electronic devices.