In the current research, we developed and printed by fused-filament fabrication polylactide-polyethylene-oxide blended membranes. The influence of relative content of polymers on the ease of extrusion and printing processes was studied. Ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethane-sulfonyl)imide (Pyr 14 TFSI) with dissolved LiTFSI salt was infused into the membranes to produce free-standing films of quasi-solid polymer electrolytes. The printed membranes were characterized by ESEM, DSC, XPS, NMR and EIS methods. Neat-printed PLA (polylactide) membrane exhibited poor wetting and low uptake of ionic liquid. However, the XPS tests of 3D-printed PLA-PEO membrane infused with LiTFSI solvated ionic liquid show evidence of the interaction between lithium cations with both, PEO (polyethylene oxide) and PLA. The measurements of diffusion coefficients by PGSE-NMR suggest that the Li + ions are coordinated by the PEO segments in the polymer blend. Increase of the PEO content at the expense of PLA polymer, leads to more than one order of magnitude improvement of bulk conductivity, approaching 0.2 mS cm −1 at 60 ° C .