Biomass is a clean, renewable and abundant resource that can be converted to bio-char, bio-oil and fuel gas through various thermochemical processes. Conversion of biomass for high value products is an important development direction for biomass utilization, which has attracted more attention. In this study, a new method of biomass pyrolysis with exogenous nitrogen introduced was proposed. The influence of NH3 on the property of bamboo pyrolysis process and products characteristics was investigated with variant approaches (e.g. elemental analysis, automatic adsorption equipment, X-ray photoelectron spectroscopy and CHI760 electrochemical workstation) and as well as the influence of KOH (as activator). The results showed that, the specific surface area, the content of nitrogen and nitrogen-containing functional groups of bio-char increased significantly with NH3 introduced in. On the other hand, with the addition of KOH, the yield of bio-char increased obviously and it increased gradually with increasing KOH amount, and the specific surface area increased dramatically to 1873.17 m2 g-1. The content of nitrogen in bio-char increased greatly with KOH introduced in, especially the content of pyridinic-N and pyrrolic/pyridone-N, while it decreased slightly with increasing KOH amount, but nitrogen content was still relative high (9.1-10.4 wt.%). The formation mechanism of nitrogen-containing functional groups was proposed. Besides, electrochemical analysis showed that the specific capacitance of bio-char electrodes increased with increasing KOH content, and the largest specific capacitance could reach to 187 F g-1 at 1 A g-1 with good cycling stability. Therefore, it could be concluded that biomass nitrogen-enriched pyrolysis was a promising method for more efficient utilization of biomass resources.