The aim of this study was to investigate the effect of oyster shell powder (OSP) and rice husk ash (RHA) on the pyrolysis of rice husk (RH) for bio-oil. The present study focuses on the effect of catalysts on pyrolysis of RH for bio-oil and the quantity of bio-oil produced. The results showed that both OSP and RHA could improve the yield and quality of bio-oil, and the catalytic effect of OSP was better than that of RHA. With the content of the two catalysts increased, the net increase range of bio-oil yield decreased gradually. With 3 wt.% of OSP or 2 wt.% of RHA, the yield of bio-oil achieved to 57.06% and 56.07% respectively, which increased by 6.03% and 4.20% compared to that of single pyrolysis of rice husk. Both OSP and RHA can increase the bio-oil heating value and decrease the acid value. With the presence of 1-5 wt.% of OSP or RHA in the RH pyrolysis process, the heating value of the bio-oil can be increased by 5.04-10.25% and 4.32-5.78%, the acid value of the bio-oil can be decreased by 5.30-13.54% and 9.81-33.01%, respectively. OSP was better than RHA on the heating value improvement, while RHA was superior to OSP in decreasing the acid value. The gas chromatography/mass spectrometry (GC-MS) analysis of bio-oil composition indicated that the formation of phenols, acids and ketones compounds were inhibited and alcohols and furan compounds were promoted with the addition of OSP and RHA catalysts. The study made the catalytic pyrolysis process more favorable for the production of high heating value fuel.