The intensity and the direction of electron flow across chloroplast extract bilayer membranes are modified by the presence of biliproteins. Biliproteins including C-phycocyanin, phycoerythrin, aliophycocyanin, and Chroomonas phycocyanin enhance the photosensitivity of the membranes. The photoelectric spectra of the membranes in the presence of biliproteins correlate with the absorption spectra of these biliproteins. Experiments are presented to demonstrate the specific character of the electron-directing ability of biliproteins. A possible mechanism involving the interaction between the biliproteins and the membranes is proposed.Photoelectric effects of bilayer lipid membranes (BLM) have been a subject of increasing interest in recent years (1-15). Such membranes containing the appropriate pigments are photosensitive if a gradient in redox potential, pH, or electric potential is created across the membrane (10). The photoelectric spectrum of BLM has been correlated with the absorption spectrum of the pigment in the membrane-forming solution (7).Studies of membranes containing photosynthetic pigments, such as chlorophyll and ,8-carotene (5, 9, 15), chlorophyll and xanthophyll (1, 2), and chloroplast extract from spinach (1, 3, 7, 10, 16), have generated a great deal of interest because of their potential as model systems for the investigation of photosynthesis and solar energy conversion (17). The major problem in the use of these membranes as models is that, in general, the photoelectric effect simply represents a dissipation of a preexisting electrochemical gradient. Ideally, model membrane processes involving electron flow across the membrane should lead to storage of some of the quantal energy absorbed by the membrane in the form of a chemical redox potential.The use of an extrinsic protein to modify the photoelectric behavior of chloroplast extract membranes (11,14) in a manner similar to the energy storage qualities of photosynthesis and solar energy cells has been reported. The purpose of this investigation is to present experiments with a number of biliproteins to expand the original observations and to demonstrate the specific electron-directing properties of these proteins.Phycocyanin and phycoerythrin, algal biliproteins, are localized in the stromal area between the thylakoid membranes and exist in the form of large discrete aggregates