A new polydiacetylene oxyphenylboronic acid (PDA-OPBA-1) bearing group was synthesized and showed diverse colorimetric changes, such as yellow, orange, and red, upon the addition of cationic surfactants at pH 7.4. On the other hand, anionic surfactants and simple ammonium salts did not show any color change. Specifically, color changes to yellow for cetyl trimethylammonium chloride (CTAC), red for dodecyl trimethylammonium bromide (DTAB), orange for benzylcetyldimethylammonium chloride (BCDA), and dark orange for hexadecylpyridium bromide (HDPB) are observed, respectively. Different head groups and alkyl chain lengths of cationic surfactants can be intelligently distinguished via a unique penetration process.