A rapid and non-destructive method was used to discriminate between calligraphies by means of Fourier transform infrared (FTIR) and FT-Raman spectroscopy in this paper. In order to discriminate two real calligraphies of Ouyang Zhong-shi from two counterfeit ones, the authors investigated the inkpad and the rice paper of the calligraphies by means of FT-Raman spectroscopy and tested the inkpad and the ink mark of the calligraphies by means of FTIR spectroscopy. It could be seen that the tiny, delicated varied chemical components of the real and the counterfeit calligraphies lead to different characters in vibration frequencies of IR and Raman functional groups and also the real calligraphies have the perfect reiteration. So the authors can discriminate between the real and the counterfeit calligraphies. It is proved that FTIR and FT-Raman are useful in the non-destructive identification of calligraphies and more precise and quicker than traditional approaches.