Structure and association of asphaltenes from coal direct hydroliquefaction were studied by fluorescence spectrometry and UV-Vis absorption spectrometry in this paper. The results indicate that asphaltene is aromatic mixtures mainly containing naphthalene nucleus and shows strong fluorescent characteristic. The forming of exciplex between asphaltene and solvent results in the red shift of fluorescence peak and fluorescence quenching of asphaltene that increases with the polarity and electron acceptability. The self-aggregation of asphaltene is formed by non-covalent bond interaction, so that the asphaltene liquefied at higher temperture that shows high aromaticity has stronger association than that liquefied at lower temperature. Aggregation of asphaltene has been found to be a gradual process, in which there is no critical aggregation constant observed, and the inflection point of the plot of apparent fluorescence intensity as a function of asphaltene concentration varies with the excitation wavelength.