Abstract Small-angle X-ray and small-angle neutron scattering studies have been carried out on poly(vinyl chloride) (PVC), and blends of PVC with solution-chlorinated polyethylene (SCPE) and poly(butyl acrylate) (PBA). The PVC used was commercial (suspension-polymerized) or bulk-polymerized. The blends of PVC with PBA were prepared by solvent-casting and those with SCPE by in situ polymerization. PVC samples show shoulders in the scattering spectra, presumably due to crystallites, which persist even in samples which have been solvent cast. Blends of PVC with PBA also show a peak but at a higher ‘ d’ spacing. The blends with SCPE which were prepared by in situ polymerization show no such peak. This suggests that the method of preparation prevents the formation of crystallites. An increase in scattering of the PBA blends was observed when the samples were heated to the temperature of phase separation. Neutron scattering studies were also carried out using 2% deuterium labelled PVC in PVC and in the blends. In the PVC this showed chain dimensions in good agreement with predicted values. In the blends, dimensions of the same order were obtained, confirming a molecular dispersion of chains in the single phase, but there was an apparent reduction in the chain dimensions. This could be explained by a true reduction in dimensions or a non-zero A 2 value in the blends.