TOF-SIMS has been widely used for characterization of various industrial materials, especially for analysis of surface contamination with its benefit of extremely high sensitivity. However, interpretation of the spectrum becomes more and more difficult when the real samples of industry with complicated surface composition must be analyzed. We have investigated factors that may influence sensitivities of adsorbed species on a well-defined silicon surface and organic polymers with different functional groups. As for silicon, oxide thickness dependence of secondary ion yields from adsorbed organic species has been demonstrated using a graded-etched SiO2 sample. In contrast, this oxygen effect of ion yield enhancement has not been necessarily observed in the system of various polymers with deposited metals. Ionization probabilities of metals on polymers may be largely affected by the interaction among functionalities of the surface. (C) 2002 Elsevier Science B.V. All rights reserved.