PVDF/(PEI‐C/PAA)n functional membranes were prepared by layer‐by‐layer (LbL) assembly, and their heavy metal ions adsorption capability was investigated. The changes in the chemical compositions of membrane surfaces were determined by X‐ray photoelectron spectroscopy (XPS). XPS results show that the surface of the PVDF membrane can be alternatively functionalized by PEI‐C and PAA. The membrane surface hydrophilicity was evaluated through water contact angle measurement. Contact angle results show that the surface hydrophilicity of the membrane surface depends on the outermost deposited layer. Morphological changes of membrane surfaces were observed by scanning electron microscopy (SEM). The water fluxes for these membranes were elevated after modification. The performances of the PVDF/(PEI‐C/PAA)n membranes on the adsorption of copper ions (Cu2+) from aqueous solutions were investigated by inductively coupled plasma (ICP). The results indicate that the PVDF/(PEI‐C/PAA)n functional membranes show high copper ions adsorption ability. Copyright © 2010 John Wiley & Sons, Ltd.