AbstractMultiple metal ions are traditionally detected using inductively coupled plasma mass spectrometry (ICP‐MS) and atomic fluorescence spectrometry. Although these methods are sensitive and accurate, they depend on complex instruments and require highly trained operators, making low costly rapid detection challenging. It is urgent to develop a convenient, rapid and sensitive method to detect multiple metal ions. Herein, we designed a bispyrene derivative (BP) with aggregation‐induced enhanced emission (AIEE) property to construct a high fluorescent sensor array to realize the effective identification of four metal ions (Fe3+, Cu2+, Co2+ and Cd2+). The differential coordination capability between metal ions and BP with the aid of acetate ions resulted the possibility of array‐based sensing. The four heavy metal ions could be immediately classified in the concentration of 100 nM. The limit of detection (LOD) of Fe3+, Cu2+, Co2+, and Cd2+ were as low as 16.2, 21.8, 51.4, and 25.9 nM, respectively. Furthermore, the sensor array was applied for identification multiple heavy metal ions in environmental samples and iron ion in rat serums with identified of 100%. The sample consumption as low as 2 µL for each detection and the results could be extracted by smartphones under ultraviolet lamps. It provided a rapid, sensitive, low‐cost, and on‐site multiple metal ions detection method.