Rhodamine 6G is doped into the photoresist which is made by mixing the 2-benzyl-2-(dimethylamino)- 4′-morpholino-butyroph and Pentaerythritol triacrylate. A 3×3 micro hexagonal pyramid array is fabricated based on the technology of femtosecond two photons by using the above photoresist. The height and length at the bottom of the hexagonal pyramid are 39 μm and 20 μm , respectively, the period of the micro hexagonal pyramid array is 60 μm. When the sample is irradiated by the 532 nm green laser, compared with the sample without Rhodamine 6G, an emission peak is found around the wavelength of 550 nm. When compared with the spectrum of the Rhodamine 6G, it is found that the peak is caused by the microstructure doped with the Rhodamine 6G. The diffraction of the sample is measured, the difference of the period between the prediction from the diffraction of the sample and designed value is 2.3%.