Poly(vinyl alcohol) (PVA)/sodium alginate (ALG)/organic rectorite (OREC) composite nanofibrous mats are fabricated by electrospinning aqueous solutions with different mixing ratios. Both good fiber shape and three-dimensional structure of nanofibrous mats can be observed by Field Emission Scanning Electron Microscopy. Energy-dispersive X-ray spectroscopy shows the existence of OREC in the as-spun composite mats. In addition, small-angle X-ray diffraction confirms that the interlayer of OREC is intercalated by ALG/PVA chains, and the distance between OREC interlayers is increased from 4.50 to 4.74 nm. Wide angle X-ray diffraction and Fourier transform infrared spectra further verify the intercalation is between polymers and layered silicate. Moreover, the thermal gravimetric analysis shows that the addition of OREC has only a small effect on the thermal stability of composites. Furthermore, the antibacterial experiments illustrate that OREC can enhance the bacterial inhibition ability of nanofibrous mats against Escherichia coli and Staphylococcus aureus.