The authors describe the use of a photosensitive polyelectrolyte to effect photoregulation of the structure and permeability of phosphatidylcholine vesicle membranes. Experimental results show that the binding of hydrophobic polyelectrolytes, e.g., PEAA, to phosphatidylcholine membranes causes large changes in membrane permeability. The results also show that the association of synthetic polyelectrolytes with phosphatidylcholine membranes can be rendered sensitive to light. Photo-controlled polyelectrolyte adsorption can thus be used to effect large changes in the structural organization, and the permeability, of bilayer membranes in water.