The fluorescence characteristics of coal macerals can be used as one of the indexes to evaluate the properties of coking coal. In this work, a single-wavelength laser with a wavelength of 360 nm was used as the excitation source to excite the surface of particulate block under a polarizing microscope. Effect of excitation time on fluorescence characteristics of the macerals was studied. The relationship between spontaneous fluorescence intensity and the excitation time of each maceral of six kinds of coking coals show that the fluorescence characteristics of coal macerals are related to the type and metamorphism of coal. The excitation time has a certain effect on the fluorescence parameters of the macerals. By comparing the relative fluorescence intensity values under different excitation times, it is found that the mean relative fluorescence intensity within 15 s can be used as an optical parameter to characterize the structure and metamorphic grade of different macerals. The essence of this method is to express movement of electrons in outer layer of nucleus by macroscopic fluorescence spectrum and relative fluorescence intensity of the initial state value and simplify microscopic complexity into macroscopic and numerical form generally accepted.