According to the present disclosure, a method for synthesizing hollow poly(vinylidene difluoride) microspheres is provided. The method, comprises the steps of (i) adding a first non-solvent to a polymer solution comprising poly(vinylidene difluoride) dissolved in an organic solvent to form a ternary mixture without inducing phase separation of the poly(vinylidene difluoride), and (ii) contacting the ternary mixture with a second non-solvent to induce phase separation to thereby form the hollow poly(vinylidene difluoride) microspheres. According to the present disclosure, a hollow poly(vinylidene difluoride) microsphere comprising a hollow core and a shell layer surrounding the hollow core, wherein the shell layer consists of poly(vinylidene difluoride) and comprises an external surface having no apertures that extend from the external surface towards the hollow core is also provided. A film comprising a plurality of hollow poly(vinylidene difluoride) microspheres obtained by the method as described above dispersed on at least one surface of a substrate is also disclosed herein.