The phase behavior and the ionic conductivity of ionic liquids (ILs) of the N-alkyl-N-alkylpyrrolidinium (PYRxy) cation and the bis(trifluoromethanesulfonyl)imide (TFSI) anion are investigated upon addition of LiTFSI salt. We compare the case of two new ILs of the PYR2y cation (where 2 is ethyl and Y is butyl or propyl) with that of the PYR14 (where 1 is methyl and 4 is butyl). We find that the addition of LiTFSI increases the glass transition temperature, decreases the melting temperature and the heat of fusion and, in the ILs of the PYR2, family, suppresses crystallization. In the solid state, significant ionic conductivities are found, being as high as 10(-5) S cm(-1), strongly increasing with Li+ concentration. The opposite trend is found in the liquid state, where the conductivity is on the order of 10(-3)-10(-2) S cm(-1) at room temperature. A T-g-scaled Arrhenius plot shows that the liquid-state ionic conductivity in these systems is mainly governed by viscosity and that the fragility of the liquids is slightly influenced by the structural modifications on the cation.