sensors. [ 17,18 ] IOM can be readily fabricated using colloidal crystal ball or fi lm as the template, followed by fi lling the solution of the framework material or its precursors into the voids of the colloidal crystal array, and then removing the original colloidal crystal template by wet chemical etching or calcination. A great variety of inverse opal materials have been prepared using this method [ 14,[19][20][21][22][23] after the fi rst report was published on Nature in 1997. [ 24 ] At the same time, the application of IOM has been extensively studied. Recently, the application of IOM in the preparation of inorganic microparticles has attracted much more attention, [25][26][27][28][29] because the monodispersed voids in IOM can be used as the ideal uniform microreactors or micromolds to obtain various particles with narrow size distribution, including metals, [ 27 ] oxides, [ 30 ] carbonates, [ 31 ] and polymers. [ 32 ] The target microparticles can be easily collected by dissolving or thermally decomposing the IOM This work reports a simple and effi cient preparation method of an inverse-opal-like macroporous polytetrafl uoroethylene (IO-PTFE) fi lm with a reusable matrix. At fi rst, the pH-responsive poly(acrylic acid) (PAA) is grafted on the PTFE latex particles induced by γ-ray radiation. The stability of PAA grafted PTFE latex particles (PTFE-g -PAA) in water decreases in acid aqueous solution. As a result, PTFE-g -PAA particles can coprecipitate with monodispersed polystyrene (PS) microspheres from the acidic aqueous dispersion to form a composite particulate fi lm. After the composite particulate fi lm is etched with toluene to remove PS microspheres, a selfstand inverse-opal-like macroporous PTFE fi lm can be successfully obtained. The macroporous PTFE fi lm can be applied as the microreactor to synthesize uniform TiO 2 particles. The separation of TiO 2 microparticles and the recycle of PTFE-g -PAA particles can be simultaneously achieved simply in water by means of ultrasonifi cation. The prepared TiO 2 microparticles also show good photocatalytic performance. This work opens a new thought to prepare special macroporous polymeric materials, and expands the microsynthesis of inorganic or organic microparticles by taking advantage of polymeric macroporous materials.