The mechanism of the collapse process of monolayers of poly-L-alanine and of its mixtures with poly-y-methyl-L-glutamate was studied at the water/air interface at temperatures of 15 ~ 20 ~ 25 ~ and 30 ~ From measurements of the collapse surface pressure as a function of molar ratios and from the determination of the collapse kinetics, as well as from ellipsometrical measurements of the thickness of the film, the complete solubility of the components, even in the collapsed phase, was deduced.Furthermore, activation energies and values ofAG*, AH*, and AS* in relationship to the kinetics of this process were deduced; it was shown that this process is constituted of a first phase of nucleation and of a second phase of growth both for the poly-L-alanine alone and for its mixtures with poly-y-methyl-L-glutamate.