Silica/polypyrrole nanocomposites without dopant (SiO2/PPy) and with oxalate dopant (SiO2/PPyOx) were synthesized using polymerization of pyrrole in the presence of nano SiO2. Synthesized SiO2/PPy and SiO2/PPyOx were characterized by FTIR, SEM, TEM and EDX and their electrical conductivities were determined by CV method through the two-point-electrode without electrolyte. The corrosion protection performance of polyvinylbutyral (PVB) coatings containing SiO2/PPyOx was evaluated and compared with that of pure PVB coatings and of PVB coatings containing SiO2/PPy by electrochemical impedance spectroscopy and adhesion measurement. The results show that electrical conductivities of SiO2/PPy and SiO2/PPyOx were 0.181 and 0.109 S/cm, respectively. The ratio of PPy on SiO2 in SiO2/PPy and SiO2/PPyOx composites was 0.77/1 and the ratio of oxalate on PPy in SiO2/PPyOx composite was 1.24/1. SiO2/PPy and SiO2/PPyOx improved corrosion resistance and adhesion of PVB coatings. The presence of oxalate in SiO2/PPyOx significantly enhanced the effect of SiO2/PPy on the protection performance of PVB coatings.