Electrospinning, self-assembly, and phase separation are some of the techniques available for the synthesis of nanofibers. Of these techniques, electrospinning is a simple and versatile method for generating ultrafine fibers from a wide variety of polymers and polymer blends. Poly L-lactide (PLLA) and Poly (vinyl alcohol) (PVA) are biodegradable and biocompatible polymers which are mainly used for biomedical applications. Nanofibrous membranes with 1:9 ratio of PLLA to PVA (8 to 10 wt % and 10 wt %) were fabricated by electrospinning. The percentage porosity and contact angle of PVA in the PLLA-PVA nanofibrous mat increased from 80 to 83% and from 39 +/- 3 degrees to 55 +/- 3 degrees, respectively. The water uptake percentage of PVA nanofibers decreased from 190 to 125% on the addition of PLLA to PVA in the PLLA-PVA nanofibrous mat. The nanofiber morphology, structure and crystallinity were studied by Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD), respectively. The thermal properties were studied by thermogravimetric analysis (TGA) and differential scanning calorimetery (DSC). The biocompatibility studies of PLLA-PVA blend were performed using fibroblast cells (NIH 3T3) by MTT assay method. The release of Curcumin (0.5, 1.0, and 1.5 wt %) from PLLA-PVA blend was found to be approximate to 78, 80, and 80%, respectively, in 4 days. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013