The π-A isotherms of a series of hexacyclolinear polyorganosiloxanes with varying molecular masses were studied. All the studied polymers are capable of forming a monomolecular layer on the surface of the water, and its collapse upon compression proceeds through the formation of discrete multilayers. Such behavior is closely related to the ability of these polymers to form a stable mesophase, although the polymers contain no mesogenic groups. It was found that, on the one hand, molecular mass does not affect the detachment of polymer macromolecules from the surface of the water and, on the other hand, markedly influences the formation of ordered multilayers.