The observed rate of drug release from a polymeric drug delivery system is governed by a combination of diffusion, swelling and erosion. It is thus not a simple task to determine the effects of the polymer on the observed drug release rate, because the swelling characteristics of the polymer are inferred from the drug release profile. Here we propose to use solution calorimetry to monitor swelling. Powdered polymer samples (HPMC E4M, K4M, K15M and NaCMC, both alone and in a blend) were dispersed into water or buffer (pH 2.2 and 6.8 McIlvaine citrate buffers) in a calorimeter and the heat associated with the swelling phenomena (hydration, swelling, gelation and dissolution) was recorded. Plots of normalised cumulative heat (i.e. q t /Q, where q t is the heat released up to time t and Q the total amount of heat released) versus time were analysed by the power law model, in which a fitting parameter, n, imparts information on the mechanism of swelling. For all systems the values of n were greater than 1, which indicated that dissolution occurred immediately following hydration of the polymer. However, while not suitable for determining reaction mechanism, the values of n for each polymer were significantly different and, moreover, were observed to vary both as a function of particle size and dissolution medium pH. Thus, the values of n may serve as comparative parameters. Properties of the polymer blends were observed to be different from those of either constituent and correlated with the behaviour seen for polymer tablets during dissolution experiments. The data imply that solution calorimetry could be used to construct quantitative structure–activity relationships (QSARs) and hence to optimise selection of polymer blends for specific applications.