Semiconductivity of passive films on steam generator (SG) tubing alloys, Alloys 690 and 800, in simulated crevice chemistries containing lead and sulphur was investigated using the Mott-Schottky analysis. The interaction of the above species with other ions on the properties of passive film and the correlation between the semiconductivity and the breakdown of passive film were discussed. Experimental results revealed that semiconductivity could be either n or p type semiconductor; both Pb and S can incorporate into the passive layer, depending on the solution pH and alloy compositions. For n type semiconductors formed on Alloy 800, they are easily broken down but more resistant to anodic dissolution; for p type passive films formed on Alloys 690 and 800, they are not easily broken down but more prone to anodic dissolution. It is concluded that the semiconductivity of passive film on SG tubing alloys was dependent on the alloy compositions, the solutions, temperature and film formation potentials.