AbstractFractionation of partly hydrolysed polyvinyl acetate (PVA) was performed by warming of its aqueous solutions. The following properties of the obtained fractions were determined: viscosity, molecular weight and molecular weight distribution, surface tension, and absorbance in the IR range. The blockiness of the polymer molecules, characterized by their behaviour towards iodine‐containing systems such as I2,‐H3BO3 and I2,‐KI, was estimated. Fractionation of the aqueous solutions of PVA by warming is based mainly on the different internal molecular structure of the separated products, i.e. on the length of the vinyl acetate blocks in the PVA molecules and, to a lesser extent, on the degree of hydrolysis and the degree of polymerization. The more blocklike are the PVA molecules, the less compatible are the polymers in the PVA‐hydroxypropyl methylcellulose (HPMC)‐water system. At phase separation in this sytem the PVA molecules which are not compatible with HPMC are, in the first place, those of the highest blockiness.