Silicon dioxide-based nanocomposites have shown great potential in novel chemical and biological sensor development due to their large loading capacity and high surface area to volume ratio for trapping molecular complexes of various sizes. However, their potential applications in forensic science, latent fingerprint detection in particular, were still unclear. In this study, we have succeeded in trapping the highly fluorescent and photo-stable Eu3+ metal ions/sensitizer complex in silicon dioxide-based nanocomposites, doped xerogels, using the sol–gel method. We have tested the spectroscopic properties of Eu3+ in several combinations of rare earth sensitizers and different derivatives of silicon dioxide nanoporous templates. Our results indicated that the use of 1,10-phenanthroline (OP) sensitizer in tetraethoxysilane (TEOS) template provides the best fluorescently doped xerogels applicable for latent fingerprint detections on various forensic relevant materials, including metal foil, glass, plastic, colored paper, and a green tree leaf. The fabrication procedure, UV/vis and fluorescence characterizations, and fingerprint labeling results of these new Eu3+/OP/TEOS nanocomposites are presented in this exploratory study.