Melt mixed blends of binary poly(vinyl alcohol) (PVOH)/ionomer, Zn2+ and PVOH/ionomer, Zn2+/polyolefin ternary blends were characterized, the former in the complete composition range, using mechanical, thermal, spectroscopic and morphology techniques. Ionomer, Zn2+ was a partially neutralized poly(ethylene-co-methacrylic acid-co-isobutylacrylate) terpolymer and the polyolefins used were high density and linear low density polyethylenes. The binary blends showed good tensile properties at high ionomer contents and this was attributed to complexation reactions at the PVOH/ionomer interphase. Thus, it was possible to use the ionomer as a compatibilizing agent for PVOH/polyolefin blends, which were characterized using most of the above techniques. Morphology studies of the ternaries at increased polyolefin compositions revealed a stratified structure, making its applicability as a barrier structured blend feasible.