Micro/nanoporous films have found use in many applications ranging from electronics or photonic to biotechnology. The preparation of such porous structures usually requires of the templates that need to be removed upon film preparation. As an alternative, the breath figures approach has been employed for the preparation of porous surfaces and films. This approach, the topic of this chapter, has several advantages over other techniques including the use of water as template (easily removed) and possibility of controlling the chemical composition of the pore and the external surface. Herein, the strategies reported to prepare honeycomb structured porous films by the breath figures approach are summarized. In addition, the methodologies reported to control the chemical composition of the porous films are depicted. The last part of this chapter focuses on the applications in which these films have been employed.