Heterocyclic nitrogen compounds play a vital role in luminescent materials, but most of them face the challenges of aggregation-caused quenching (ACQ) and poor water solubility. In this work, we present the nitrogen heterocyclic pentaphenylpyrrole (PentaPP) with an excellent aggregation-induced electrochemiluminescence (AIE-ECL) performance in the aqueous phase through the comparison of the elegant ECL luminophore 5,10,15,20-tetraphenylporphyrin (TPP). Further studies suggest that such unique AIE-ECL arises from its propeller-like noncoplanar structure and the large conjugation from the phenyl groups on the ring. In addition, the new ECL analysis could feature some advantages of AIE characteristic, water compatibility, and strong signal and finally achieve the ultrasensitive detection toward the explosive 2,4,6-trinitrophenol (TNP) with a lower detection limit (1.1 nM). This study does not only benefit to solve the two key problems mentioned before but also enriches the fundamentals and applications for ECL and pyrrole research.