The behavior of several phenylalanyl dipeptides in a mixed ethylene glycolaqueous buffer solvent has been studied by spectroscopic techniques, and definite evidence for a concentration-dependent self-interaction has been obtained for these systems. Of particular interest is the observation of gel formation, suggestive of linear aggregation, for N-benzyloxycarbonyl-l-phenylalanyl-l-phenylalanine and for l-methionyl-l-phenylalanine under suitable conditions of concentration, temperature, and mixed solvent composition. This evidence of aggregation is in accord with theoretical considerations of the structure of biopolymers. © 1969.