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We report a facile method to synthesize a series of WO 3 microfibers with three-dimensional architectures of nanoparticles and/or microplates through an infiltration and calcination process by taking cotton as template. The crystal structures, morphologies and optical properties of the WO 3 microfibers have been investigated systematically leading to the finding that the WO 3 microfibers show mixed phases and delicate micro/nano-structures which can be controlled by calcination temperature and rate. Furthermore, we also find that the WO 3 microfibers calcined at 500 °C under a calcination rate of 1 °C/min exhibit an intense photoluminescence emission around 452 nm. [ABSTRACT FROM AUTHOR]