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Luminescent poly(methyl methacrylate) (PMMA) porous fibers were prepared by electrospinni-ng technology using a binary solvent system of EA/DMF and DCM/DMF. The effects of the ambient humidity, content of rare earth complex (Tb(phen)L3)，molecular weight of PMMA, and the proportion of E-A/DMF (mass ratio) on the pore formation of the fibers were investigated. The morphology, structure, surface area, and luminescent properties of porous luminescent fibers were characterized. Results showed that when using EA/DMF as mixed solvent system, the solvent ratio has great influence on the pore formation of fibers comparing to the effect of environmental humidity. PMMA fibers with higher molecular weight only have pores on the surface, while relative low molecular weight's fibers have pores both inside and on the surface. The addition of Tb(phen)L3 can improve the morphology of fibers, but the excess will hinder the formation of pores. Due to the effect of porous formation, the surface area of fiber mat increased by 113 m2/g. The as-prepared fibers have good luminescent properties, and high specific surface area. The change in fluorescence intensity affected by water and oil has potential application in oil water separation indicator.