Orientation of amorphous, miscible poly(vinyl phenol) (PVPh)-poly(ethylene terephthalate) (PET) blends is studied using experimental and modelling techniques. Up to 50 wt% PVPh, the blends are semi-crystalline and were therefore not studied. At 60 wt% PVPh, no crystallisation was observed using either differential scanning calorimetry or X-ray diffraction. For the 60wt% PVPh blend, FTIR dichroism determination showed that orientation was relatively high (0.09 at a lambda = 3.4) and similar for both polymers. Above 60 wt% PVPh, however, no appreciable orientation was detected. In order to gain insights about the deformation phenomena in polymer blends, atomistic models of the 60 wt% PVPh composition were built using the Meirovitch approach. These were found in good agreement with X-ray diffraction, and exhibit a fair degree of interpenetration as estimated visually and by comparing intermolecular pair distribution functions. Significant hydrogen bonding was found: 8% of carbonyl oxygens and 1% of carboxylate oxygens of PET are bound to PVPh. Deformation simulations were performed using the Parrinello-Rahman deformation scheme. Orientation of PVPh and PET in the blend was found equivalent to that observed in pure polymers simulations. PET orientation followed the aggregate model and was more oriented than PVPh by a factor of two. It was concluded that the similarity in orientation of the two polymers in the blend, which was observed experimentally on quenched samples, could be due to a combination of different deformation-induced orientation followed by distinct relaxation mechanism and relaxation times for both polymers. (C) 2003 Elsevier Ltd. All rights reserved.