X-ray photoelectron spectroscopy (XPS) is a widely used technique to characterize the surface chemistry of materials. It plays a crucial role in accessing qualitative and quantitative information and in detecting the presence of chemical functional groups on the surface of any material. The forensic methods available to detect and identify elements and organic/inorganic compounds are often destructive, so evidence cannot be re-analyzed. However, XPS allows rapid analysis of samples without damaging them. Recently, an increasing number of forensic researchers have begun to study certain chemical information on fingermarks. In this study, the authors aimed to present the applicability and power of XPS imaging in fingermark analysis which can also provide specific information about the fingermark chemical composition. Herein, monochromated X-ray (Al K alpha) spot size was fixed at 50 mu m. XPS mapping resulted in the acquisition of spectra at each pixel, in an array of 41 x 30 pixels with a step size of 50 mu m. Then, a simple discussion has been made about how the scanned surface spectrum and basic snapshot spectra are used to identify different components at a fingertip of a scanned surface area (similar to 3 mm(2)). Hence, a fingermark pattern contaminated with caffeine, TiO2, and Pb/PbO deposited on the silicon wafer can be chemically mapped and visualized by XPS using principal component analysis (PCA). Thus, the present study showed the possible applicability of XPS for the identification of illicit drugs of abuse, gunshot residue, and skin care products on latent fingermark by mimicking a crime scene evidence.