This study investigated the degradation characteristics and biodegradability of phenol, refractory organic matters, by injecting MgO and CaO-known to be catalyst materials for the ozonation process-into a Dielectric Barrier Discharge (DBD) plasma. MgO and CaO were injected at 0, 0.5, 1.0, and 2 g/L, and the pH was not adjusted separately to examine the optimal injection amounts of MgO and CaO. When MgO and CaO were injected, the phenol decomposition rate was increased, and the reaction time was found to decrease by 2.1 to 2.6 times. In addition, during CaO injection, intermediate products combined with Ca2+ to cause precipitation, which increased the COD (chemical oxygen demand) removal rate by approximately 2.4 times. The biodegradability of plasma treated water increased with increase in the phenol decomposition rate and increased as the amount of the generated intermediate products increased. The biodegradability was the highest in the plasma reaction with MgO injection as compared to when the DBD plasma pH was adjusted. Thus, it was found that a DBD plasma can degrade non-biodegradable phenols and increase biodegradability.