A new molecule, (Z)-4-(4-(dimethylamino)benzylidene)-3-methyl-1-(pyridin-2-yl)-1H-pyrazol-5(4H)-one (dmpp), and its novel heteroleptic iridium(III) complex, [(ppy)2Ir(dmpp)]PF6, were synthesized and characterized. Both dmpp and [(ppy)2Ir(dmpp)]PF6 could be used as highly selective and sensitive chemodosimeters for the cyanide anion by the naked eye, owing to the addition of the CN− to the vinyl group of dmpp. The addition of CN− to a solution of dmpp induced a change in the solution color from yellow to colorless, and to [(ppy)2Ir(dmpp)]PF6 induced a change in the solution color from pink to colorless. Moreover, [(ppy)2Ir(dmpp)]PF6 could also act as a phosphorescent and electrochemical probe of CN−. The green phosphorescence band at 520 nm and a new irreversible oxidation wave at 0.423 V showed up upon the addition of CN−, indicating that [(ppy)2Ir(dmpp)]PF6 was an excellent multisignaling chemodosimeter of CN−. Importantly, the Ir complex-based cyanide chemodosimeter [(ppy)2Ir(dmpp)]PF6 has much easier and faster detection of CN− than pure organic molecule dmpp.