To give guidance for producing bamboo charcoal, chemical composition and cellulose crystallinity of moso bamboo with different natural stacking time of 1 and 2 months were determined. The co-pyrolysis characteristics of control or stacked bamboo and Chinese fir were investigated by thermogravimetric analysis. Results showed that natural stacking pretreatment changed chemical composition of moso bamboo and decreased cellulose crystallinity. The lignin content of B0, B1 and B2 was 27.56%, 30.70% and 25.36%, respectively. The crystallinity of cellulose was 40.15% of B0, 40.09% of B1 and 37.79% of B2. Even though pyrolysis process of all samples was similar, natural stacking pretreatment, mixing ratios and heating rates had a significant impact on their pyrolysis characteristics. But the synergistic interactions were not found during co-pyrolysis process. B1 had the highest char yield of 22.95%, which gradually increased with increase in B1 content of blends. 60%B1/40%W had the lowest activation energy (Ea) at all conversion rates, which was suggested to use as raw materials of charcoal.