Taking advantages of both the well-known α,β-unsaturated structure and the special nucleophilicity of organic amines toward its acceptor moieties, intramolecular charge transfer as a signaling mechanism is used to design and synthesize a new ratiometric chromophoric fluorescent probe (BI-CA-ID) with large emission shifts toward organic amines. This probe is employed for the detection of organic amines with high selectivity and sensitivity and a “naked-eye” color change (from red to colorless). Ultraviolet–visible and fluorescence spectrometric measurements are used to determine detection limits as low as 0.024 and 0.43 μM. Furthermore, nucleophilic addition of the amine on the α,β-unsaturated of BI-CA-ID indicated that the sensing mechanism occurs via interruption of the π-conjugation.