Even though poly(ethylene oxide) (PEO) is immiscible with both poly(L-lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with L-lactide (LLA) through ring-opening polymerization to obtain a poly(vinyl alcohol)graft- poly(L-lactide) (PVA-g-PLLA) brush copolymer with 82 mol % LLA according to H-1 and C-13 NMR spectroscopies. PEO has been blended with the PVA-g-PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self-concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA-g-PLLA blends. (C) 2016 Wiley Periodicals, Inc.