The work aims to prepare fluorine-containing hydrophobic coatings and improve overall performance of the coatings. With mixed powder with Al2O3∶PFA mass ratio of 4∶1 and 3∶1 as thermal spraying powder, PFA/Al2O3 composite hydrophobic coatings were prepared on aluminum substrate by adopting atmosphere plasma spraying (APS). Phase composition, microstructure, bonding strength, microhardness, hydrophobic properties, etc. of the coatings were evaluated, respectively. Technological parameters were adjusted to prepare different coatings, and structure and performance of the coatings were compared. Based on characteristics and deposition states of the two kinds of particles in plasma flame flow, the effects on the hydrophobic properties were discussed and analyzed. The coatings were mainly composed of γ-Al2O3, there was a small fraction of α-Al2O3 microcrystals or amorphous crystals in the coatings as well. Surfaces of different coatings exhibited certain hydrophobicity, static water contact angle of the surfaces reached over 100°, bonding strength reached over 23 MPa, and microhardness could be up to 760 HV0.3. Hydrophobicity of the coatings made from mixed powder with mass ratio (Al2O3∶PFA) of 3∶1 is improved significantly, indicating that the content of F element on the surface is an important factor affecting hydrophobicity. However, both bonding strength and microhardness of the coatings decline. The two kinds of powder particles are heated by flame flow and then deposited on substrate in molten or semi-molten state, forming a aggregated tabular composite structure. At the same time, some unmelted or semi-molten ellipsoid particles are detected on the surface and periphery of tabular structure.