In this paper, 2D asynchronous spectra generated by using the DAOSD approach was utilized to probe interactions between Nd3+ and pyridinium dissolved in aqueous solution. A series of cross peaks in the resultant 2D asynchronous spectrum confirms the occurrence of intermolecular interaction between Nd3+ and pyridinium. However, no coordination occurs between Nd3+ and pyridinium. Interaction between π electron from aromatic system and f electron from lanthanide ions account for the appearance of cross peaks in 2D asynchronous spectra. Because of the interaction, the emission spectrum of pyridinium exhibits a significant change when neodymium perchlorate was introduced into the system.