In this study, we report on the effect of Bioglass (R) structural transformations on its sintering behaviour. While heating up to 1000 degrees C, five successive transformations occur: glass transition, glass-in-glass phase separation, two crystallization processes and a second glass transition. The sintering of the material exhibits two main shrinkage stages associated with the two glass transitions at 550 and 850 C. At 580 degrees C, the glass-in-glass phase separation induces a decrease in the sintering rate immediately followed by the major crystalline phase crystallization (Na2CaSi2O6) between 600 and 700 degrees C, from the surface to the bulk of the particles. A complete inhibition of sintering takes place followed by a minor shrinkage effect due to crystallization. A plateau is then observed until the second glass transition temperature is reached. A modification of Frenkel's model allows the determination of the glass-in-glass phase separation kinetics and the identification of the structural transformations effects on sintering behaviour.