Separation-free analytic techniques capable of providing precise and real-time component information are in high demand. ¹⁹F NMR-based chemosensing, where the reversible binding between analytes and a ¹⁹F-labeled sensor produces chromatogram-like output, has emerged as a valuable tool for the rapid analysis of complex mixtures. However, the potential overlap of the ¹⁹F NMR signals still limits the number of analytes that can be effectively differentiated. In this study, we systematically investigated the influence of the sensor structure and NMR solvents on the resolution of structurally similar analytes. The substituents adjacent and distal to the ¹⁹F labels are both important to the resolving ability of the ¹⁹F-labeled sensors. More pronounced separation between ¹⁹F NMR peaks was observed in nonpolar and aromatic solvents. By using a proper sensor and solvent combination, more than 20 biologically relevant analytes can be simultaneously identified.