Bio-oil emulsions were stabilized using coconut shell coke, modified amphiphilic graphene oxide, and hydrophobic nano-fumed silica as solid emulsifiers. The effects of different particles on the stability of bio-oil emulsions were discussed. Over 21 days, the average droplet size of raw bio-oil increased by 64.78%, while that of bio-oil Pickering emulsion stabilized by three particles only changed within 20%. The bio-oil Pickering emulsion stabilized by Ni/SiO2 was then used for catalytic hydrodeoxygenation. It was found that the bio-oil undergoes polymerization during catalytic hydrogenation. For raw bio-oil hydrodeoxygenation, the polymerization reaction was little affected by the temperature below 200 °C, but when the temperature raised to 250 °C, it was greatly accelerated. However, the polymerization of monocyclic aromatic compounds in the reaction process was partially inhibited under the bio-oil Pickering emulsion system. Additionally, a GC-MS analysis was performed on raw bio-oil and hydrodeoxygenated bio-oil to compare the change in GC-MS-detectable components after hydrodeoxygenation at 200 °C. The results showed that the Pickering emulsion catalytic system greatly promoted the hydrodeoxygenation of phenolic compounds in bio-oil, with most monocyclic phenolic compounds detected by GC-MS converting to near 100%.