Crylic acid and azobenzene containing acrylate copolymers PEAPH were fabricated into multilayers with their counterpart polyelectrolyte poly(diallyldimethylammonium chloride)(PDAC)in N

N'-dimethylformamide (DMF)using the layer-by-layer electrostatic adsorption technique The self-assembly of wator soluble and insoluble PEAPH in DMF was studied and compared．FTIR was used to detect the ionization of carboxyl acid of PEAPH during the assembling processes．All results show that both the water-soluble and water-insoluble PEAPH can be deposited with PDAC based on the electrostatic attraction instoad of other interactions．In assembling processes PEAPH molecules ate deposited in molecular level instoad of molecular aggregation and form a cross-linking muhilayer structure．Assembling media of DMF and water do not have obvious infiuence on the muhilayer structure．