large high-quality zeolite MFI single crystal 3.0 x 1.5 x 1.5 mm(3) in size was synthesized by means of a nutrition supplemental method and a p-nitroaniline (PNA)/MFI single crystal was prepared via physical vapor deposition. The light yellow PNA/MFI single crystal changed to green when irradiated by 1062 nm fundamental wavelength from a Nd:YAG pulse laser, and the transmitted light includes the SHG wavelength 527 nm. Both C-H-N analysis and molecular mechanics suggested that there were five PNA molecules encapsulated in each MFI unit cell, and the structure of the PNA molecule within the MFI microporous system is noncentrosymmetric. The PNA/MFI single crystal would be potentially applied as a NLO material.