Waste woody biomass samples including poly(vinyl chloride) (PVC), which were mixed with metal hydroxides as additives, were carbonized at 500 degrees C to investigate the catalytic effect of the additives on pyrolysis products and to elucidate the mechanism of biomass carbonization. The results showed that the yield of char significantly increased, whereas tar evolution was suppressed by the influence of metal hydroxides, even with the coexistence of PVC. Moreover, the interaction behaviors between the biomass structure including PVC and metal hydroxides were further investigated. It was clarified that the dehydration reaction to form a cross-linked structure in biomass by the effect of metal ion and the neutralization reaction between PVC and metal hydroxides were simultaneously occurred during the carbonization. The presence of chlorine component, which is one of corrosive substances, was confirmed in char structure by chlorine analysis. Therefore, a flushing method with warm and cold water was applied, to investigate the possibility of chlorine removal. The results showed that flushing with warm water and cold water are both effective for the removal of chlorine component in the char. Finally, the new pyrolysis process of NaOH-mixed waste biomass materials, including proposed heat recovery facilities, can be suggested as an effective system of biomass utilization for energy savings and CO2 reduction.