Miscibility of poly(4-vinyl pyridine) (P4VP) and poly(2-vinyl pyridine) (P2VP) with poly(vinyl acetate) (PVAc), poly(vinyl alcohol) PVA and poly(vinyl acetate-co-alcohol) (ACA copolymers) has been investigated over a wide composition range. Differential scanning calorimetry (DSC) results indicate that P2VP is immiscible with PVAC, PVA, and their copolymers over the whole composition range. In turn, P4VP appears to be immiscible with PVAC and PVA, but miscible with some ACA copolymers in certain range of composition. The P4VP-ACA phase diagram for different copolymer compositions has been determined. The variation of the glass transition temperature with composition for miscible mixtures was found to follow the Gordon-Taylor equation, with the parameter kappa dependent upon copolymer composition. FTIR analysis of blends reveal the existence of specific interactions via hydrogen bonding between hydroxyl groups and the nitrogen of the pyridinic ring, which appear to be decisive for miscibility.