Analogue calorimetry for blends of poly(vinyl ester)s and polyacrylates has been studied. Hydrogenated monomers were used as analogues of the corresponding polymers. It is found that isomeric esters differing only in the orientation of the COO group mix with only small heat change, which can be positive or negative. The values of the interaction energy density, B-12 (in cal/cm(3)), are -0.045, 0.031, and -0.076, respectively, for the following binary mixtures; ethyl acetate + methyl propionate, n-propyl propionate + ethyl butyrate, and phenyl propionate + ethyl benzoate. The negative heat of mixing for the two pairs of very similar liquids, although unexpected, explains why the corresponding polymers are miscible. The small positive heat of mixing for the other pair is sufficient to predict demixing of the corresponding polymers, viz., poly(n-propyl acrylate) and poly(vinyl butyrate), which contradicts the observation of their homogeneous mixing. This suggests that hydrogenated monomers are not always the proper analogues for vinyl polymers for the prediction of the interaction energy. A novel flow calorimeter is also described. H-E and V-E data for binary mixtures of the above esters are presented.