Some block copolymers based on polymethacrylonitrile (PMAN) and polyethers or polyacetals were synthesized in an anionic way. To appreciate the salt/polymer interactions, polymer electrolytes were prepared by the dissolution of lithium imide or lithium perchlorate in PMAN homopolymer and copolymers. The investigation of the triblock copolymer complexes allowed the solvating competition between nitrile-and ether- or acetal-functional groups to be highlighted. The polydioxolane solvating ability was equivalent to that of PMAN but lower than that of polyoxyethylene or polyoxypropylene. Moreover, we were interested in the salt effect as block compatibilization was concerned. (c) 2005 Wiley Periodicals, Inc.