Silica synergistically stabilized paraffin Pickering emulsion is applied to modify wood flour (WF) for preparing wood/polymer composites. The effect of Pickering emulsion on properties of the WF and its composites with high-density polyethylene (HDPE) is investigated. The impregnation of paraffin Pickering emulsion could significantly improve the WF dispersion in HDPE matrix, resulting in increased melt flow index (MFI). It increased from 1.3 g/10 min (control) to 2.1 g/10 min (Pickering treatment) due to the lubrication of paraffin and rolling friction provided by silica nanoparticles. The hydrophobicity of the WF was improved by the penetration of paraffin and silica in the cell wall, which could consume the hydroxyl groups in WFs via hydrogen bonding. Owing to the well distribution of WFs and silica, the mechanical properties and surface hardness of the composites were enhanced obviously. The optimal tensile strength and impact strength increased 23% (18.28 MPa) and 32% (14.16 kJ/m²), respectively. It also could be attributed to the improved interfacial compatibility due to the incorporation of surfactants (Span 80 and Tween 80), which acted as a coupling agent. Furthermore, the silica incorporated in the WF could compensate the negative effect of paraffin on thermal stability of the composites. A model concerning the interactions in the composites was proposed based on the research results.