Microporous films with tunable honeycomb structures were fabricated based on the self-assembly of a series of clusto-supramolecular star polymers (CSPs) guided by breath figure templates. The CSPs consist of a hydrophilic polyoxometalate cluster core and several hydrophobic polystyrene arms that are electrostatically connected to the core, in which three Keggin-type polyoxometalate clusters [CoW12O40](6-), [SiW12O40](4-) and [PW12O40](3-) were used as the cores. The dynamic bonding character endows CSPs a rearrangeable amphiphilic conformation that facilities them to accumulate at the oil/water interface to stabilize water droplets. By precisely adjusting the arm number and arm length of CSPs, we revealed the relationship between the structure and the film-forming behavior of CSPs. Regular pores with a small diameter as low as 260 nm were obtained by optimizing the structure of CSPs. Moreover, the CSPs could act as morphological modifiers to efficiently improve the microporous regularity of polystyrene films, even at a low CSP content of 0.8 wt%. To the best of our knowledge, this is the first work using supra molecular star polymers to fabricate microporous films by the breath figure method, which not only introduces a new film-formation material, but also provides a facile way to incorporate inorganic functional components into microporous polymer films. (C) 2017 Elsevier Ltd. All rights reserved.