This work deals with the synthesis of different poly(vinyl chloride) (PVC) based block copolymers, containing poly(hydroxypropyl acrylate) segments having different compositions and molecular weights. These copolymers were synthesized via single electron transfer-degenerative chain living radical polymerization. The block copolymers prepared showed deviations from the theoretical predictions in terms of molecular weight and polydispersity, which were ascribed to the heterogeneous nature of the reaction mixture. The technical problems addressed are important to the establishment of the required technological improvements for the industrial implementation. It has been shown that the control over the composition of the block copolymers is only achieved when the amount of vinyl chloride used in the second step of the polymerization was relatively high. The adhesion performance of these block copolymers in PVC-wood flour composite formulations was studied by assessing the mechanical performance of such composites, when the copolymers were included in the composite formulations. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013