Excitation-emission orthogonalized luminescent upconversion nanoparticles (OUCNPs), which can respond to changes in external stimuli accordingly, showgreatpromisein many intelligent applications. However, the construction of such materials mostly relies on the selective absorption of Nd³⁺and Yb³⁺at different wavelengths and the long-range energy migration between the layers, resulting in complex structures and limited orthogonal luminescence intensity. Here,we developed a relatively simple structure of OUCNPs (β-NaErF₄@NaLuF₄@NaYF₄:20%Yb,2%Er@NaLuF₄), where the fluorescence emission switches from red to green when the excitation wavelength is shifted from 808 nm to 980 nm. This structure exhibits high-quality, independent and non-interfering orthogonal luminescence properties without Nd³⁺ sensitization and long-range energy migration. As a proof of concept, we demonstrate the application of the designed OUCNPs in anti-counterfeiting. We also prepared OUCNPs@PEI self-referencing fluorescent probes toenable quantitative analysis of TNT in solution with a detection limit of 3.04 μM. The probes can be made into test strips for portable on-site visual detectionofTNT, and can also be used to image latent fingerprints and detect explosive residues in fingerprints simultaneously. The concept proposed in this work can be extended to the visual detection of a larger range of organic and biological molecules,andis highly promising for practical applications.