The saving and recycling of chemical substances, which may be hazardous to human health and ecosystems, constitute a desirable goal worldwide. It is important to use a natural polymer that has a highly specific function and an environmental friendliness. In this study, humic acid was added to a natural polymer, a pectin membrane, and a hydrophobic poly(1-trimethylsilyl-1-propyne) (PMSP) membrane to enhance the affinity for phenol or aniline. Also, the separation performance, based on the membrane materials and methods of addition, was investigated. The effect of the adsorption of phenol and aniline by humic acid was investigated. A high rate of aniline adsorption was observed. The interaction of the humic acids and the aniline was mainly observed by polar bonding. For the PMSP membrane with humic acid added to the surface, the humic acid exists in a colloidal state. During pervaporation, the permeation of water was prevented by the adsorbed solute. Because the permeability of aniline increased and the permeability of water significantly decreased, the PMSP membrane with humic acid added to the surface had a high permeate aniline concentration, and the permselectivity was improved. (C) 2004 Wiley Periodicals, Inc.