A novel fabrication technique for producing hybrid organic-inorganic perovskite impregnated poly(styrene) microfibers in situ in a melt electrospinner is presented. The relationship between the hybrid perovskite precursors, electrospun fiber morphology, and chemical phase domains was investigated using light microscopy, scanning electron microscopy, x-ray diffraction spectroscopy, and energy dispersive spectroscopy. The method was successful in producing composite microfibers and revealed information regarding the nature of encapsulated hybrid perovskites under higher-than-normal temperature conditions during the synthesis and subsequent annealing process. (C) 2016 American Vacuum Society.