Differential scanning calorimetry (DSC) measurements have been carried out on a series of ABA poly(styrene-b-isoprene) triblock copolymers with 30% polyisoprene content and various molecular weights. The DSC data show an inward shift for the glass transition temperatures (Tg) of the blocks compared to the corresponding homopolymers. As a function of the molecular weight, one to three transitions were found. The additional third Tg gives some further evidence of the existence of an interphase between the microdomains.Numerous studies [1, 2] on multicomponent polymer systems have established the occurence of phase segregation and microdomain formation when two or more polymers are combined, in block copolymers, the factors governing the size of the domains depend on the number and length of the blocks and on their chemical nature.Meier [3] was the first to develop a theory about microphase formation for styrene-butadiene di-and triblock copolymers [4]. He showed that above a certain molecular weight, phase segregation takes place. Williams [5] and later Helfand [6] investigated the formation of an interphase: between the two pure phases, a region of mixed phases exists. These authors evaluated the influence of molecular weight and composition of the different blocks on the size of the pure phases and of the interphase. Particularly, the volume of the interphase increases with decreasing molecular weight. Toporowski and Roovers [7] as also Kraus and Rollmann [8] concluded that some low molecular weight block copolymers form a single phase. Through these investigations, block copolymers may exist in the solid state with morphologies going from a single phase to a completely organized two-phase structure.Glass transition temperatures (Tg) are commonly used to detect phase changes in copolymers. Two distinct Tg's corresponding roughly to those of the parent homopolymers appear when two well segregated phases exist in a copolymer. On the other hand, random copolymers known to exist as a single phase, show only one Tg, the value of which depends on its phase content. Thus, the number of transitions and the temperature at which they occur, provide information about the morphology of SIS copolymers.