Abstract-Pyrroloquinoline quinone (PQQ), an important natural product, is biosynthesized by Gluconobacter oxydans.In order to prepare the product in large scale, a rapid and selective chemical complexation extraction (CCE) is proposed to separate and purify PQQ from fermentation broth. In this work, the effect of extraction solvent system, stripping agent, and inorganic ion on the extraction were investigated, respectively. As a result, trioctylamine-octanol system showed the most extraction constants (log K ex = 5.07). Ammonia water was the most stripping agent (log K ex = 4.85). Several inorganic salts were determined to have negative effect on the extraction, which suggest that inorganic salts should be removed from broth before extraction. Finally, the optimal extraction condition is Trioctylamine-octanol system (1:1, v/v), 28 °C, and pH=6.5, which leads to more than 90% of extraction rate. In conclusion, trioctylamine-octanol system and ammonia water showed excellent extraction efficiency, which can be used to prepare PQQ.