Detection of nitroaromatic explosives especially picric acid (PA) is considerably worth concern on human safety and homeland security. Herein, we developed an effective probe (APPTPEP) for PA detection in aqueous medium by combination of 1,4-dihydropyrrolo[3,2-b]pyrrole with tetraphenylethylene and pyridine units. The incorporation of tetraphenylethylene unit in the backbone endows the APPTPEP a significant aggregation induced emission (AIE) behavior. Pyridyl group was proved as recognition site for PA and their strong interaction was confirmed by H-1 NMR titration and supported by theoretical calculation. Owing to this strong affinity, APPTPEP exhibited high selectivity and sensitivity (limit of detection 31.5 nM) to PA over other nitroaromatic compounds. This research provides new insights into the rational design of AIE-active materials for effective sensing application.