In this work, novel functionalized poly(L-lactide) (F-PLLA) porous fibers were fabricated through electrospinning using the PLLA/methylene chloride (CH2C12)/N,N-dimethylformamide (DMF) solution containing diethylenetriamine (DETA) and gamma-aminopropyltriethoxysilane (KH-550). The effects of PLLA, DETA and KH-550 contents on the morphologies of the electrospun fibers were systematically investigated, and the results showed that at PLLA, DETA and KH-550 contents of 20% w/v, 2 wt% and 3 wt%, respectively, the electrospun F-PLLA fibers exhibited the homogeneous distribution of fiber diameters and the homogeneous porous structure on the fiber surface. Nitrogen-containing groups were successfully introduced to the electrospun fibers, which induced the great improvement of the hydrophilicity of the membrane surface. Adsorption measurements showed that the electrospun F-PLLA membrane had good adsorption ability toward Congo red (CR), and the adsorption capacity at room temperature was enhanced in 16 times compared with the common PLLA fiber membrane, and the maximum adsorption capacity was 135.7 mg g(-1). Furthermore, the adsorption behavior could be well described by the pseudo second-order model. Oil/water separating measurements showed that the electrospun F-PLLA membrane exhibited high separation efficiency and the maximum water fluxes were 2018 and 1861 L m(-2) h(-1) in separating non-emulsified and emulsified oil/water system under atmospheric pressure, respectively.