Novel unsaturated polyester composites with PAN-based nanofiber, stabilized PAN nanofiber, and carbonized nanofiber webs have been fabricated, respectively, and the effects of the nanofiber web content on their electrical resistivity, the thermal stability, dynamic storage modulus, and fracture surfaces were studied. The result demonstrated that the introduction of just one single layer (which is corresponding to 2 wt.%) of the carbonized nanofiber web to unsaturated polyester resin (UPE) could contribute to reducing markedly the electrical resistivity of the resin reflecting the percolation threshold, to improving the storage modulus, and to increasing the thermal stability above 350oC. The effect on decreasing the resistivity and increasing the modulus was the greatest at the carbonized PAN nanofiber web content of 8 wt.%, particularly showing that the storage modulus was increased about 257~283% in the measuring temperature range of −25oC to 50oC. The result also exhibited that the carbonized PAN nanofibers were distributed uniformly and compactly in the unsaturated polyester, connecting the matrix three-dimensionally through the thickness direction of each specimen. It seemed that such the fiber distribution played a role in reducing the electrical resistivity as well as in improving the dynamic storage modulus.