The aim of this study is to define the condition of optimal pre-treatment for preferable activated carbon fibers (ACFs), which are based on rayon fibers. This paper shows the ideal path of ACFs preparation process; implies that rayon fibers are pre-treated by various solvents with different times before the heating process. The pre-treated rayon fibers finally turned into desirable rayon fiber-based ACFs through optimal pre-treatment condition by heating processes. The thermal analysis method of pre-treated rayon fibers by thermo-gravimetry analyser (TGA) is an idealized tool, which analyzes the best thermal condition of pre-treatment process. Surface morphologies of resulting rayon fibers based ACFs were examined by scanning electron microscope(SEM). The results of TGA and SEM analyses show that the optimal pre-treatment condition for preparing ACFs was clearly defined, in terms of thermal stability and surface morphology.