Herein, we report an efficient synthesis of two novel probes for cyanide sensing based on 7-arylpyrazolo[1,5-a]pyrimidinium salts PS (aryl = p-MeOPh) and T-PS (aryl = p-Ph2NPh). According to theoretical analyses, T-PS was found to be an ideal probe with improved absorption and emission properties due to a better intramolecular charge transfer (ICT) process. The experimental results, such as limit of detection (LOD; PS, 0.30 and 0.34 μmol/L → T-PS, 0.15, 0.15, and 0.25 μmol/L) and outstanding selectivity demonstrated the predicted properties. DFT calculations, HRMS analysis, and 1H NMR titration experiments were carried out to confirm the mechanism, regioselectivity, and reversibility of the CN– addition reaction in detecting the probes. These findings are especially attractive in the cyanide-sensing field. However, important repercussions on the sustainability performance, such as raw material costs and waste generation, were observed when comparing PS with T-PS. Satisfyingly, test strips fabricated using T-PS also demonstrated its practical applicability; in addition, emission in solid-state measurements of T-PS supported on silica showed its capability to detect cyanide ions in the solid state and in bitter almonds after 50 ppm. Ultimately, small amounts of CN– (0.5 μmol/L) in tap water detected by using the probe T-PS. Therefore, this work provides a sustainable and applicable approach in cyanide chemosensor preparation.