PFO(pyrolized fuel oil) and C10+ oil, which are the residual heavy oils form a NCC(naphtha cracking center), were heat-treated to produce the precursor-pitch for carbon materials. After PFO was initially distilled near 300℃ to separate the volatile matters recovering as high-quality fuel oil, the residuum of nonvolatile precursor-pitch was then thermally pyrolized in the temperature ranges from 350℃ to 450℃. Spinnable isotropic pitch with the softening point of 200℃ and the toluene insolubles of 36wt% was obtained at 365℃, and then was successfully spun through a spinneret(0.5mm diameter). After spinning, an isotropic carbon fiber of 25μm diameter was obtained via oxidation and craboniation procedures. Mesophase spherules began to be observed from the product pitch pyrolized at 400℃, and bulk mesophase with a flow texture was observed above 420℃. In the case of C10+ was the feed was polymerized in the presence H2SO4 at room temperature to increase the molecular weight and then heat-treated gradually up to 200~250℃. The products obtained with the softening point of 80~190℃ were carbonized at 500 and 1000℃ to examine the morphology.