Intercalated hybrid materials alternating optical nonlinear organic chromophores and inorganic Mn 2 P 2 S 6 layers were obtained by ion exchange method. The Mn 2 P 2 S 6 powder was synthesized by solution-state combined solid-state method, which benefited for MPS 3 ’s mass production. The reaction between Mn 2 P 2 S 6 layers and inserted chromophores was intensified by UV–visible spectroscopy. It was indicated that Mn 2 P 2 S 6 powders after solution-state combined solid-state method was single crystalline and DAMS molecules self-assembled in the layers of Mn 2 P 2 S 6 to form J-aggregates. Second-harmonic generation (SHG) of DAMS/Mn 2 P 2 S 6 thin films was observed by Maker fringe measurement. The DAMS/Mn 2 P 2 S 6 intercalated material was well formed by ion exchange method.