In the present study, the samples of leachate of 0, 5, 10-years-old landfill were respectively taken from landfill plant, the dissolved organic matter (DOM) was extracted from landfill leachate, and the fluorescence spectra of DOM were determined. The fluorescence synchronous scan spectra of DOM in 0-year-old leachate exhibited a primary peak at 335 nm, a secondary peak at 455 nm, and a shoulder peak at 385 nm. While the fluorescence intensities of DOM at different peaks were decreased for 5-year-old leachate, especially those of the peaks at shorter wavelengths (335 and 385 nm) which may be ascribed that the simpler structural components were decreased sharply. Compared with 5-year-old leachate, the fluorescence intensity of DOM in 10-year-old leachate decreased slightly. Three-dimensional excitation emission matrix fluorescence spectra (3DEEM) of DOM in 0-year-old leachate exhibited two peaks at Ex/Em wavelength pairs of 270/355 and 220/350, respectively, which were all associated with protein-derived compounds, while the peaks of protein-like disappeared in 5-year-old leachate, and new peaks of complex structural fulvic acid-like were formed at Ex/Em wavelength pair of 330/412.5 and 250/416.5, respectively. This indicated the component of DOM in the leachate of 5-year-old landfill led to a decrease in low molecular compound, and an increase in high molecular compound compared to that of the 0-year-old. 3DEEM of DOM of 10-year-old leachate was similar to that of DOM in the 5-year-old, but the fluorescence intensity of the peaks of fulvic acid-like in DOM was different, and compared with that of 5-year-old leachate, the peak of DOM in 10-year-old leachate shifted from Ex/Em wavelength pair of 250/416.5 to 250/427.5. This indicated that the DOM formed similar structures, but the structure of fulvic acid-like in DOM of 10-year-old leachate had a greater degree of aromatization and quantity than that of 5-year-old leachate. The results obtained from fluorescence synchronous scan spectroscopy and 3DEEM indicate that aromatic structures of DOM are enriched with the age of landfill leachate.