Abstract In the present work, photoactive cation N, N′-Dimenthyl-9, 9’-bisacridinium nitrate (BNMA) was assembled with exfoliated layered α-zirconium phosphate (α-ZrP) via an electrostatic layer-by-layer (LBL) assembly method. As a result, the luminescent films which were well-aligned and periodical had been successfully fabricated. Surprisingly, the lifetimes of (BNMA/ZrP)n were found to be prolonged by 16-fold for the first time, due to the isolation effect of inorganic nanosheets and hydrogen ion migration between the interlayers. Therefore, it is testified that α-ZrP can be used as the laminate and has remarkable influences on enhancing the lifetimes of chromophores. We expect that this new discovered effect can enable α-ZrP a kind of new potential material to develop novel light-emitting materials and optical devices.