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Poly(2‐vinyl pyridine) [P2VP] and poly(4‐vinyl pyridine) [P4VP]/copper iodide binary mixtures were studied by differential scanning calorimetry (DSC) in order to investigate the phase behavior of the blends at microscopic level. The glass transition temperature (Tg) of the P2VP/copper iodide binary mixtures as compared with pure polymer increased by 80°C when the amount of Cu(I) in the blend was increased up to 40/60 wt/wt monomer/inorganic salt composition for P2VP. For P4VP, the Tg increased by 40°C in an 80/20 wt/wt decreasing by 10°C at 60/40 wt/wt. Fourier transform infrared (FTIR) and Raman spectroscopy provided molecular‐level data, suggesting that copper coordinates with pyridine rings via nitrogen ion pairs in a metal‐ligand bonding. Conductivity measurements were carried out at different temperatures and compositions, and upon increasing the amount of copper iodine in the blends, the conductivity increased drastically. © 2000 John Wiley & Sons, Inc. Adv Polym Techn 19: 113–119, 2000

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