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A new type of conjugated polybenzimidazole (<b>CPBI</b>) was synthesized through a simple polycondensation reaction without metal catalysis, and <i>N</i>-alkylation modification was carried out to solve the problems of solubility and fluorescence properties. A series of nano-microsphere polymers <b>CPBI<i>_n</i></b> with large conjugation, good solubility, and strong fluorescence has been successfully used as “turn-off” fluorescent probes for the first time. The results show that, under suitable <i>N</i>-alkylation conditions, the obtained <b>CPBI<i>_n</i></b> can be used as a highly sensitive and selective fluorescent probe for the detection of Cu²⁺ and Zn²⁺ at the same time, and their detection limits are both nM levels. In addition, <b>CPBI₂</b> can be designed as an ultra-sensitive IMPLICATION logic gate at the molecular level, cyclically detecting Cu²⁺. With the test paper containing <b>CPBI₂</b>, easy and quick on-site detection can be achieved. This research provides a new idea for the brief synthesis of multifunctional materials.