AbstractPhenolic-rich bio-oil can be selectively produced from catalytic fast pyrolysis of biomass impregnated with K3PO4, K2HPO4, or KH2PO4. In this study, the catalytic effects of the three catalysts on the pyrolytic product distribution were investigated and compared via analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments. The results indicated that the three catalysts were all able to inhibit the pyrolytic decomposition of holocellulose to form volatile organic products, while promoting the formation of phenolic compounds from lignin. Hence, phenolic-rich bio-oil could be selectively produced. Among the three catalysts, K3PO4 and K2HPO4 possessed similar capability to increase the yield of the phenolics, which was better than KH2PO4. The phenolic contents among the total pyrolytic products steadily increased as the K3PO4 or K2HPO4 dosage increased. The maximal peak area of the phenolics reached as high as 68.8% (at 50 wt.% K3PO4) or 50.6% (at 50 wt.% K2HPO4) of the total peak area. Therefore, based on these results, K3PO4 was the best catalyst for the selective production of phenolic-rich bio-oil.