The present paper deals with the synthesis and characterization of novel polymer in salt electrolytes based on a poly(acrylamide) matrix. The effect of the type of lithium salt and its concentration on the conductivity and microstructure of the studied electrolytes is analyzed. To this end impedance spectroscopy, infra-red spectroscopy, DSC and Maldi-ToF techniques are used. The highest conductivities achieved exceeded 10(-4) S/cm at ambient temperatures. The high values of decoupling index are evidences of predominantly cationic transport in the studied electrolytes.