Pitch precursors were synthesized from coal tar(CT) and pyrolysis fuel oil(PFO, petroleum residue oil) at relatively low temperature of $250^{circ}$, in the presence of horontrifluorideidiethyletherate complex(BFDE) as a catalyst and nitrobenzene(NB) as a co-catalyst. The softening point, nitrogen content and carbon yield increased with an increase of concentration of NB. The pitch precursors with good spinnability were prepared by removing the volatile components through $N_2$ blowing. The precursor pitches were spun through a circular nozzle, stabilized at $310^{circ}$ and finally carbonized at $1000^{circ}$. The optically anisotropic structure formed at the absence of NB was changed into isotropic structure, showing a decrease in size of the flow domain. The hollow carbon fiber could be prepared in the process of stabilization. The results proposed that the morphology of carbon materials could be controlled by changing the concentration of catalyst and/or co-catalyst and/or stabilization condition that affect on the mobility of molecules during carbonization.