To investigate the possible chemical structure of monomeric constituents originated from the depolymerzation of humic substances, an optimization of analytical tool, capillary zone electrophoresis, was established first. Amixture sample of eleven supposed phenolic monomers were prepared and well separated in 80 mM borate buffer, pH 9.0, at 20 kV. After the depolymerization in a sealed stainless-steel bomb, CuO catalysis, and consequent solvent extractions, the degradation products of the five nature humic substances and two synthetic ones were all analyzed in the electrophoreic condition. Besides, humic substance samples were scanned in the spectroscopic and elemental analysis to preliminarily screen the relative average molecular mass, oxygen content, and degree of aromatic content. Comparison between electropherograms and spectrum are made.