The invention relates to a pillar[5]arene / isophthalic acid-1,8-naphthalenedicarboximide complex. The complex uses copillar[5]arene as a subject, isophthalic acid-1,8-naphthalenedicarboximide as an object and C-H...PI and electrostatic force as driving force; and a part of isophthalic acid-1,8-naphthalenedicarboximide with negative charges is included into the cavity of copillar[5]arene through self-assembling in an alkaline environment, so the process of assembling of the subject and the object is finished. After aluminum ions are added into a solution of the pillar[5]arene / isophthalic acid-1,8-naphthalenedicarboximide complex, the fluorescence of the complex solution is enhanced and yellow fluorescent light is given out; and when anionic CN<-> is further added, the fluorescence of the complex solution undergoes a red shift and green fluorescent light is given out. Therefore, the pillar[5]arene / isophthalic acid-1,8-naphthalenedicarboximide complex is applicable as a novel supramolecular fluorescence sensor for continuous detection of Al<3+> and CN<-> in environment.