X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry were used to investigate the aging effects on the aminopropylsilane (APS) and quaternary ammonium surfactant-treated mineral fibers. APS-coated mineral fiber samples were treated with cationic surfactant and mineral oil and aged at 70 °C temperature and 95% humidity. From quantitative XPS measurements, an increase in the atomic composition of oxygen, nitrogen, and silicon is observed after aging. An increase in the protonated amino groups in the N1s high-resolution spectra and C–N group in the C1s high-resolution spectra is also observed. These results indicate that the concentration of hydrocarbon groups decreases after aging due to the partial removal of the long hydrocarbon chains of the surfactant and mineral oil and/or hydrolysis and segregation of APS to the fiber surface. The principal component analysis (PCA) was applied to the time-of-flight secondary ion mass spectrometry spectra, and an increase in the intensities of APS characteristic peaks were observed after aging. The observed increase in the signals of APS originates from underlying silanized fibers after the removal of the surfactant and mineral oil from the surface. Copyright © 2012 John Wiley & Sons, Ltd.