Nanofibers of poly(vinyl alcohol) (PVA)/layered double hydroxide (Mg-Al LDH) composites are prepared by the electrostatic fiber spinning using water as the solvent at a high voltage of 21 kV. Either inorganic LDH carbonate (LDH-CO3) or L-lactic acid-modified LDH (Lact-LDH) is used for incorporating with PVA. Scanning electron microscopy SEM investigations on the nanofibers suggest that the average diameters of PVA/LDH composite fibers are smaller than that of neat PVA. Transmission electron microscopy (TEM) investigations indicate that the dispersity of the LDH in PVA matrix is much improved after modification with L-lactic acid. The mechanical properties of the PVA/LDH fibers are obviously enhanced compared to that of neat PVA. For example, the tensile stress and elongation at break of the PVA/Lact-LDH electrospun fibrous mat with 5 wt % Lact-LDH are 31.7 MPa and 36.7%, respectively, which are significantly higher than those of neat PVA, and also higher than those of PVA/LDH-CO3 owing to the better dispersity of Lact-LDH nanoparticles. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012