AbstractBisphenol‐A polycarbonate (PC)/poly(methyl methacrylate) (PMMA) blends (PC/PMMA) were prepared by melt mixing with and without a trans‐esterification catalyst (tetrabutylammoniun tetraphenylborate), which is able to promote inter‐exchange reactions between PC and PMMA. Evidences of the ester–ester exchange reaction taking place were pointed out via Fourier Transform Infra‐Red and size exclusion chromatography analyses. A series of enthalpy relaxation measurements were carried out for the pure polymers and for blends thereof. The data were analyzed on the basis of the Tool–Narayanaswamy–Moynihan/Kohlraush–Williams–Watts model. This model characterizes the structural relaxation in the glass transition region by means of four parameters: the apparent activation energy (Δh*), the nonlinearity (x), the nonexponentiality (β), and the pre‐exponential factor (τ0). The apparent activation energy can be determined from the cooling rate dependence of the fictive temperature (Tf) measured using DSC. Δh* values of homogeneous blend and of the starting polymers were determined in this way, while an estimation of x, β and τ0 was proposed. Comparisons were made between a single glass transition temperature PC/PMMA blend and homopolymers data. The experimental values of Δh* suggest that the degree of cooperativity decreases on going from the starting polymers to the blend. POLYM. ENG. SCI., 47:218–224, 2007. © 2007 Society of Plastics Engineers.