Poly(vinyl pyrrolidone) (PVP)/La3+/Zr4+ precursor nanofibrous membranes (LZPNM) with various Zr contents were synthesized via a simple electrospinning method. By controlling the Zr incorporation, the tensile properties of precursor membranes dramatically change from 0.77 to 1.73 MPa. Meanwhile, the average diameters of precursor nanofibers increase with the increase of Zr contents (from 283 to 535 nm). In addition, flexible La2O3ZrO2 nanofibrous membranes (LZNM) were obtained by calcination of corresponding precursor membranes. Furthermore, the structures and morphologies of the precursor membranes were investigated using X-ray powder diffraction analysis (XRD) and field-emission scanning electron microscopy (FE-SEM). The surface functional groups and thermal properties of the precursor membranes were measured via Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA).