The excitation energy (3.4 eV) and emission energy (2.7 eV) of 9-ethynyl-9-hydroxyanthrone (EHAO) were obtained from time-dependent theoretical functional theory (TDDFT) and single-excitation configuration interaction (CIS) method. The effects of CH₃OH and TNT on the fluorescence spectrum of 9-ethynyl-9-hydroxyanthrone were described by the front orbital theory. Results show that the electronic transition of the first excited state of the EHAO-CH₃OH complex only occurs in the EHAO moiety,while the fluorescence properties were changed. In the complex of EHAO and TNT, HOMO is located in EHAO, and LUMO in TNT molecule. It suggests that intermolecular electron transfer occurs during the transition of the first excited state,which results in the fluorescence quenching effect.