A dihydroxy-substituted tricyanopyrroline-based near-infrared (NIR) colorimetric probe (TCP-34Hy) is developed for the effective detection of fluoride ions in aqueous medium in the presence of Ca2+ ions. The naked-eye detection (drastic color change) selectively makes the NIR colorimetric sensor more efficient. The probe can detect fluoride ions from inorganic sources (NaF/KF) as well as organic sources (TBAF) in water. The water samples from different sources, such as tap, pond, river, and sewage, have been tested successfully for fluoride ion detection using the probe (TCP-34Hy). Investigations of different kinds of soil samples (clay soil, red soil, and river sand) after pre-treatment with NaF are also productive for detection of fluoride ions in water. The probe can also detect fluoride ions in toothpaste in aqueous medium. The role of Ca2+ is discussed and explained on the basis of experimental results. Additionally, the probe (TCP-34Hy) shows high selectivity towards fluoride ion detection with a LOD of 2.3 μM (0.052 ppm) in aqueous medium.