In this work, we have employed an intramolecular charge transfer-based DMN colorimetric probe for the rapid naked-eye detection of cyanide ions in solution as well as real water samples. The intermolecular interaction between the DMN probe and cyanide ions in solution was investigated using a combination of spectroscopic and computational methods in this study. The DMN probe exhibited a selective colorimetric response for cyanide ions over the other anions exposed. The cyanide sensing mechanism of the probe has been investigated by 1H NMR titration and density functional theory calculations. The results reveal that the colorimetric response of the DMN probe is due to the Michael adduct formation in the β-conjugated position of the dicyanovinyl group with cyanide, which blocks intramolecular charge transfer transition. Under optimized experimental conditions, the DMN probe showed a linear plot in the concentration range of 0.01-0.25 μM, with a detection limit of 23 nM. Further, a 3D printed portable accessory for the smartphone and an open-source android application is developed to suit the DMN probe for on-site work. In addition, we have developed the microfluidic paper-based analytical device that could selectively detect cyanide ions at very low concentration using a colorimetric DMN probe. In addition, the DMN probe was effectively used to determine the cyanide ion in a variety of water samples.