A six-branched chlorophyll a biosynthetic pathway instead of a four-branched pathway has been proposed as being responsible for the formation of chlorophyll a in green plants. The several biosynthetic routes that make up the pathway have been described as leading to the formation of ten chemically different groups of chlorophyll a species. The latter differ from one another by one or more of the following modifications: (a) by having a vinyl or ethyl group at position 4 of the macrocycle, (b) by the nature of the long-chain fatty alcohols at position 7 of the macrocycle, and (c) by having a 6-membered lactone ring instead of a 5-membered cyclopentanone ring. The chemical structure of several of the metabolic intermediates of that pathway and of some of the chlorophyll a species have now been determined by primary chemical derivatization methods coupled to spectrofluorometric, nuclear magnetic resonance and mass spectral analyses. The formation of highly organized photosynthetic membranes in which some of the chlorophyll alpha molecules are specifically oriented is ascribed to the multiplicity of chlorophyll biosynthetic routes which result in the formation of multiple chlorophyll alpha chemical species. Proper orientation of chlorophyll in the photosynthetic membranes is visualized as being controlled by peripheral group modifications that either modulate the polarity of the Chl chromophore or control the magnitude of the net positive charge on the central Mg atom. Finally it is proposed that in addition to the proper orientation of chlorophyll a, chemical heterogeneity of the chlorophyll chromophores in the photosynthetic reaction centers is mandatory for efficient charge separation, and proper vectorial electron transfer.