Three dissolved organic matter (DOM) samples were obtained from municipal solid wastes at the initial (C0), high-temperature (C7) and mature (C51) period during composting. Two-dimensional correlation spectroscopy (2D-COS) analysis on Fourier-transform infrared (FTIR), ultraviolet visible (UV-vis), and synchronous fluorescence spectra (SFS) were used to investigate the metal binding properties of compost-derived DOM. Synchronous and asynchronous maps of 2D-FTIR-COS of DOM-Cu(II) and DOM-Pb(II) were similar, however, the susceptibility and binding sequence of the corresponding spectral region was different. The N-H (amide I), phenolic OH, and C-O of alcohols, ethers, and esters were the most susceptive in the C0, C7, and C51 samples, respectively. 2D absorption COS indicated that the preferential binding with Cu(II) was shown to be at 305 nm for C0, at 236 nm for C7 and C51, and with Pb(II) at 247 nm for C0, at 233 nm for C7 and C51. 2D-SFS-COS indicated that protein like matter showed a higher susceptibility and preferential binding with Cu(II) than humic-like substances. DOM showed a higher complexing affinity with Cu(II) than Pb(II) on the basis of the log K values. Spectral techniques combined with 2D-COS are useful to understand the binding heterogeneities of ligand sites within DOM-Cu(II) or Pb(II) during the composting.