Honeycomb-structured porous films have been widely applied in various industrial areas such as chemical sensors, tissue engineering, and micro reactors. In this article, one novel self-assembly approach is proposed to fabricate well-ordered polyphenylene oxide honeycomb films by a facile control of spraying ultrasonic humidifier atomized water droplets. Proper spraying retention time is necessary for porous films formation with highly uniform pore size. The effect of atomized water droplets flux on the pore size and the regularity of the hexagonal arrays were experimentally investigated. The pore size became larger with increasing the solution concentration. Especially, honeycomb films with two-level pores were fabricated by spraying atomized water droplets two times and the influence of interval time on the two-level honeycomb films formation was investigated. Apart from analysis of structural characteristics, self-assembly mechanism was also discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41163.