The thermal properties of organic membranes attract much attention due to the fact that heat dissipation in electronic devices limits their functionality and reliability. Here, we enhance the thermal conductivity of polyvinyl alcohol (PVA) membrane using nano-fibers fabricated by electrospinning. Measured by the 3-Omega method, the results show that the effective thermal conductivity of the electrospinning membranes (with/without Cu nanoparticles) are as high as 0.7 W/m-K at room temperature which is as twice as the value of thermal conductivity of amorphous spin-coated PVA membrane (0.35 W/m-K). The mechanism of enhancement are that, compared with amorphous membrane, the phonon scattering is attenuated and the crystallinity is improved in the electrospinning process. Our studies bring new insights in designing new kind of membrane with high thermal conductivity.