Two azole silane couple agents TUP and IAP were synthesized from 3-isocyanatopropyltriethoxysilane, 2-aminothiazole and imidazole. Organometallic coatings were obtained by dipping method on copper foil surface using TUP and IAP as main film-forming agents applied in high-frequency PCB, and then compared with brown oxidation film and polymeric coatings containing KH132 and KH580. The structure, surface morphology, flatness and hydrophobicity of the films were characterized by FTIR, SEM, AFM and contact angle measurement, respectively. The corrosion resistance of the layers was evaluated by electrochemical, salt spray and saline immersion tests, and the interfacial adhesion between copper foil and epoxy resin was investigated after laminates process. The results indicated that two azole silane coupling agents were both successfully grafted onto the copper surface, fabricating relatively smooth and compact organic protective films. The organometallic coatings formed by TUP with a concentration of 3% (based on the total mass of ethanol and water) exhibited excellent smoothness with Ra and Rq both below 21 nm，optimal hydrophobicity with water contact angle up to 142°. Furthermore, the corrosion inhibition efficiency could reach 99.2% and salt spray resistance up to 14 d revealing best barrier performance. In addition, the peel strength of copper/resin laminates achieved 5.97 N/cm appropriately, satisfying interfacial adhesion requirement of PCB.