The intermolecular hydrogen bonding interactions between poly(3-hydroxybutyrate) and poly(styrene-co-vinyl phenol) copolymers with mutual solvent epichlorohydrin were thoroughly investigated by steady-state fluorescence and viscosity techniques. Fluorescence spectroscopy along with viscosity technique was used to asses the intermolecular hydrogen bonding between poly-(3-hydroxybutyrate) and its blends with five copolymer samples of styrene–vinyl phenol, containing different proportions of vinyl phenol but similar average molecular weight and polydispersity index. In the case of very low OH contents (2–4 mol %), as expected, both components of poly(3-hydroxybutyrate) and poly(styrene-co-4-vinylphenol) chains are well separated and remain so independently of the mixed polymer ratio and overall polymer concentration as well. Conversely, when the OH content reaches 5.8 mol % or more, a significant decrease of the intrinsic fluorescence intensity emitted by the copolymer is detected upon addition of aliquots of poly(3-hydroxybutyrate). In these cases, an average value for the interassociation equilibrium constant, KA = 8.7, was obtained using a binding model formalism. A good agreement of these results with those obtained from complementary viscosity measurements, through the interaction parameter, Δb, was found. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 900–910, 2006