Miscibility and intermacromolecular complexation between poly(styrene-co-4-vinylphenol)(STVPh) and poly(ethyl methacrylate)(PEMA) have been studied by means of differential scanning calorimetry (DSC) combined with physical aging and non-radiative energy transfer (NRET) fluorospectroscopy. Toluene which is inert to hydrogen bonding

was used as the casting solvent. Only 1 mol% hydroxyl content in STVPh was found to be able torender its iscibility with PEMA. When the hydroxyl level of STVPh was found to be able torender its iscibility with PEMA. When the hydroxyl level of STVPh is progressively increased

Tgs of the blends approach and ven exceed the values calculated from Fox equation

and the transitions become narrower. Besides

in the NRET measurements

the blends show far higher energy transfer efficiency compared with the ordinary miscible blends. All these facts indicated the complex formation between the two polymers. It was also observed that the casting solvent substatially affects the miscibility and complexation. When THF was used as the casting solvent

due to its proton-accepting ability

it partially destroied the hydrogen bonding between STVPh and PEMA in solutions and consequently hidered the miscibility in bulk. It was found that for the THF-cast blend

Tgs are 5～10K lower than those calculated from Fox equation

and the NRET efficiency is always olwer than that of corresponding toluenecast noes.