Silicon carbide(SiC) exhibits many unique properties, such as high strength, corrosion resistance, and high temperature stability. In this study, a SiC-fiber web was prepared from polycarbosilane(PCS) solution by employing the electrospinning process. Then, the SiC-fiber web was pyrolyzed at $1800^{circ}C$ in argon atmosphere after it was subjected to a thermal curing. The SiC-fiber web (ground web)/phenolic resin (resol) composite was fabricated by hot pressing after mixing the SiC-fiber web and the phenolic resin. The SiC-fiber web composition was controlled by changing the fraction of filler (filler/binder = 9:1, 8:2, 7:3, 6:4, 5:5). Thermal conductivity measurement indicates that at the filler content of 60%, the thermal conductivity was highest, at 6.6 W/mK, due to the resulting structure formed by the filler and binder being closed-packed. Finally, the microstructure of the composites of SiC-fiber web/resin was investigated by FE-SEM, EDS, and XRD.